US20040011252A1

US20040011252A1 - Non-toxic corrosion-protection pigments based on manganese

Info

Publication number: US20040011252A1
Application number: US10/341,435
Authority: US
Inventors: Jeffrey Sturgill; Andrew Phelps
Original assignee: Individual
Current assignee: University of Dayton
Priority date: 2003-01-13
Filing date: 2003-01-13
Publication date: 2004-01-22
Also published as: US7789958B2; US20070149673A1; WO2004065305A1; AU2003298785A1

Abstract

Corrosion-inhibiting pigments based on manganese are described that contain a trivalent or tetravalent manganese/valence stabilizer complex. An inorganic or organic material is used to stabilize the trivalent or tetravalent manganese ion to form a compound that is sparingly soluble, exhibits low solubility, or is insoluble in water, depending upon the intended usage. Specific stabilizers are chosen to control the release rate of trivalent or tetravalent manganese during exposure to water and to tailor the compatibility of the powder when used as a pigment in a chosen binder system. Stabilizers may also modify the processing and handling characteristics of the formed powders. Manganese/valence stabilizer combinations are chosen based on the well-founded principles of manganese coordination chemistry. Many manganese-valence stabilizer combinations are presented that can equal the performance of conventional hexavalent chromium or tetravalent lead systems. It is emphasized that this abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to commonly assigned U.S. patent application Ser. No. ______, (Attorney Docket No. UVD 0318 PA) NON-TOXIC CORROSION—PROTECTION PIGMENTS BASED ON PERMANGANATE AND MANGANATE, filed Jan. 13, 2003 by Sturgill et al., the disclosure of which is incorporated herein by reference.[0001]

BACKGROUND OF THE INVENTION

This invention relates generally to compositions and methods for the formation of protective, corrosion-inhibiting pigments without the use of chromium in the hexavalent oxidation state or lead in the tetravalent oxidation state. More particularly, this invention relates to non-toxic, corrosion-inhibiting pigments based on trivalent and tetravalent manganese and methods of making and using the same.

Inhibiting the initiation, growth, and extent of corrosion is a significant part of component and systems design for the successful long-term use of metal objects. Uniform physical performance and safety margins of a part, a component, or an entire system can be compromised by corrosion. Aluminum, zinc, iron, magnesium, titanium and their alloys tend to corrode rapidly in the presence of water due to their low oxidation-reduction (redox) potentials. The high strength 2000 and 7000 series of aluminum alloys are used extensively in aircraft and are very sensitive to corrosive attack. Materials such as steels and carbon fibers with higher redox potentials will form a galvanic couple in water and promote corrosive attack when located near light metal alloys such as aluminum.

A bare metal surface or one that has been conversion coated, phosphated, sealed, rinsed, or otherwise treated will be protected by the application of a primer paint with a corrosion inhibiting pigment. As used herein, the term “pigment” means chemically active compounds with the ability to inhibit corrosion at a distance, rather than simple colorants or opacifiers. Oxidative compounds that are effective as corrosion inhibitors tend to be highly colored and/or opaque. An effective corrosion inhibiting pigment has throwing power and can protect exposed base metal in a scratch or flaw by oxidizing and passivating it at a distance during aqueous corrosion when dispersed in a suitable carrier phase. These compounds are usually solids or liquids that are typically dispersed in a liquid carrier or binder system such as a paint or wash. These compounds may also be used to help inhibit corrosion without a significant liquid carrier using an integral binder and/or a low-volatile application method. Barrier layer formers such as sol-gel coatings or polymeric films are also used, but they tend to have no inherent oxidizing character and no appreciable throwing power and fail to protect the metal surface when the film is breached.

Pigments that contain hexavalent chromium (CrVI) compounds are the de facto standard for high-performance corrosion inhibiting paints and coatings for metal protection and are a typical corrosion inhibitor used to protect aluminum, zinc, magnesium, iron, titanium, copper and their alloys. Zinc (C.I. Pigment Yellow 36) and strontium (C.I. Pigment Yellow 32) chromate pigments are typically used, although higher-solubility calcium and magnesium chromates have also seen some limited use as pigments. The coating vehicles of these pigments include alkyd-type primers, acrylic primers, and elastomeric sealants, among others. Some transition metal chromate pigments (e.g., complexed with copper, iron, manganese, or cobalt) and organic chromate pigments (e.g., bound with nitrogenous compounds such as guanidinium) have been used in protective coating systems. Barium or lead chromates have also been used as corrosion inhibitors, as well as colorants. Variations in chromate speciation (i.e., what the chromate ions are bound to) will result in significant differences in protection when used as corrosion-inhibiting pigments, due to differences in chromate solubility.

A clear correlation between performance and solubility of chromate pigments has been shown. However, oxidizing chromates can be dangerous to use as corrosion inhibitors if they are not delivered in sufficient quantity in a timely manner to the location of a coating breach. The chromate composition was far more important to the corrosion inhibiting performance of the primer film than the organic coating composition.

A principle use of zinc and strontium chromate pigments is in wash- or etch-primer formulations for aluminum protection. Wash- or etch-primers, which have been used since the 1940s, represent one of the harshest application conditions for chromate pigments. Wash-primers are applied to metal surfaces under acidic conditions where the primer is cured as a corrosion inhibiting film. Chromate pigment powders dispersed in an alcohol/resin base mixture are combined with an aqueous phosphoric acid diluent solution. The acid roughens the metal surface and initiates cross-linking of the resin to form a pigment-filled polymeric film. The chromate pigment may also be dispersed in other carriers that are not as harsh as the wash primer. However, if a corrosion-inhibiting pigment can survive the harsh conditions of acid diluent, then it can usually be successfully incorporated within other paint, polymeric, or barrier film systems for corrosion inhibition.

An important use of chromate pigments is in coil coating formulations for steel, zinc-coated steel, or aluminum sheet stock. Coil coatings can represent a challenging application environment for pigments in that cure temperatures for these paints can exceed 100 C. Corrosion-inhibiting pigments for these applications must exhibit both throwing power to inhibit corrosion and be thermally stable at elevated temperatures when incorporated into the paint.

Lead chromate pigments of various compositions are mostly used as colorants, although they are also used for corrosion protection, albeit often for different applications than zinc or strontium chromates. This is necessitated by the much lower solubility of lead chromate in comparison to these other chromates. The dark yellow lead chromate (PbCrO ₄, C.I. Pigment Yellow 34) exhibits a solubility of approximately 10⁻⁷moles/liter Cr⁺⁶, whereas the darker basic lead chromate (PbCrO₄.PbO, C.I. Pigment Orange 21) exhibits slightly lower solubility in water. In addition, lead chromate can be combined with other lead compounds to alter the spectral or solubility characteristics. For example, the lemon yellow lead silicochromate (PbCrO₄.PbSiO₃) and reddish lead molybdate-chromate (PbCrO₄.PbMoO₄, C.I. Pigment Red 104) are representative examples. [Note: This same situation exists for zinc chromate pigments such as ZnCrO₄, ZnCrO₄.Zn(OH)₂, and ZnCrO₄(OH).Zn(OH)₂, wherein increased basicity leads to lowering of the solubility.]

While lead chromate can be used in some of the same coating vehicles as zinc or strontium chromate (i.e., alkyd-type primers), the much lower solubility of lead chromate permits its use in binder systems for which zinc or strontium chromate would be unsuitable. For example, lead chromate is often used in oil-based paints (i.e., linseed oil) wherein greater than 75% by weight of the paint system is pigment. The mechanistic action of the divalent lead ion present in the lead chromate pigments is discussed below.

Pigments that contain tetravalent lead (PbIV) are also used extensively in coatings for metal protection, especially for steels and cast irons. The most notable PbIV pigment is red lead (Pb ₃O₄, C.I. Pigment Red 105). Red lead is compositionally equivalent to lead plumbate [(Pb²⁺)₂(PbO₄4⁴⁻)], wherein only one of the constituent lead atoms is in the tetravalent oxidation state, while the other two are present as the more common divalent species. The PbVI solubility for this compound is a remarkably low 10⁻¹⁷moles/liter Pb⁺⁴(Glasstone, J. Chem. Soc. 121: 1456-69, 1922), implying an extremely low release rate of PbIV. Red lead is used primarily in alkyd-type primers as well as oil-based paints such as those containing linseed oil.

Calcium plumbate (Ca ₂PbO₄, Caldiox™) is another representative example of a corrosion-inhibiting pigment containing PbIV. Due to its higher solubility in comparison to red lead, calcium plumbate is most frequently used for applications where a quicker release of oxidizing ions is necessary for protection, such as on galvanized steel. Calcium plumbate is most frequently used in alkyd-type or acrylic primers.

The use of hexavalent chromium or tetravalent lead pigments allows a broad range of service conditions to be addressed by tailoring the solubility of the pigment to the application needs. Very low solubility pigments, such as red lead, employ other corrosion-inhibiting mechanisms in addition to oxidative passivation. The divalent lead ions present in red lead (and even lead chromate) have been observed to form “lead soaps” after long storage when the pigment is used in conjunction with oil paints, especially those comprised of linseed oil. “Lead soaps” are reaction products between the alkaline divalent lead ions and the long-chain carboxylic acids present (i.e., oleates, linoleates, linolenates, palmitates, and stearates). This indicates that even though these pigments exhibit low solubility in water, the constituent ions are still chemically active, but less than their more soluble cousins. The divalent lead ions form insoluble compounds with corrosive anions such as sulfate, and low-solubility compounds with other corrosive ions such as chloride, thereby effectively removing them from the corroding system. For the heavier, more insoluble lead pigments such as red lead and basic lead chromate, the inhibiting action is due to both the oxidative tetravalent lead or hexavalent chromium ions, and the ability of the divalent lead ions to ‘capture’ (insolubilize) corrosive anions such as sulfate.

Significant efforts have been made in government and industry to replace CrVI and PbIV with other metals for corrosion-inhibiting applications due to toxicity, environmental, and regulatory considerations. An effective replacement for hexavalent chromate or tetravalent lead pigment needs to have throwing power for self-healing coating breeches. Throwing power is the ability of a highly oxidized ion, such as hexavalent chromium or tetravalent lead, to oxidize and passivate the exposed bare metal in a small scratch or flaw.

A number of materials have been introduced as corrosion-inhibiting replacement pigments for tetravalent lead- or hexavalent chromium-based compounds. Commercially available corrosion inhibiting pigments including compounds such as molybdates, phosphates, silicates, cyanamides, and borates that have no inherent oxidizing character have been used as alternatives to chromate pigments. Coatings that contain these materials can effectively inhibit corrosion as barrier films until the coating is breached, as by a scratch or other flaw. Films or coatings that do not contain oxidizing species can actually enhance corrosion on a surface after failure due to the effects of crevice corrosion.

Manganese is one non-toxic, non-regulated metal which has been considered as a chromium or lead replacement. Manganese (like chromium or lead) exhibits more than one oxidation state (Mn ⁺², Mn⁺³, and Mn⁺⁴). In addition, the oxidation-reduction potential is comparable to that of CrVI or PbIV in acidic solutions. For example, in acid solution:

Mn⁺³+e⁻

Mn⁺²+1.49 V

Mn⁺⁴+e⁻

Mn⁺³+1.65V

Cr⁺⁶+3e⁻

Cr⁺³+1.36 V

Pb⁺⁴+2e⁻

Pb⁺²+1.70 V

The MnIV and MnIII ions are very good oxidizing species with oxidation-reduction potentials of +1.65 V and +1.49 V (at pH 0), respectively. The hydroxyl and oxygen liberated from water when MnIV or MnIII is reduced will oxidize nearby bare metal. This results in a passivated metal surface if sufficient oxygen is released. The potential required to reduce tetravalent or trivalent manganese to divalent manganese is only 0.29 or 0.13 volts greater than that needed to add three electrons to reduce CrVI to trivalent chromium (CrIII). Although neither MnIV or MnIII match PbIV in terms of redox potential, neither is significantly lower and so comparable passivation of metal is achieved. MnII is formed during corrosion inhibition by the oxidation of base metal in the presence of MnIV or MnIII and water. MnII is similar to CrIII in that neither is particularly effective as redox-based corrosion inhibitors.

A number of pigments using manganese have been reported in the literature over the years, but none approach the general performance or utility of PbIV- or CrVI-based pigments. For example, Manganese Violet is a colorant composed of MnII pyrophosphate with no oxidizing characteristics.

A number of compounds have been described as corrosion-inhibiting agents, including organic mercapto and thio compounds, cyclic tetraaza compounds, aminophosphonic acid, and triazinedithiols and triazinetrithiols. Other compounds have been described as corrosion inhibiting when complexed with manganese, typically in the divalent charge state. Among these compounds are porphyrin derivatives, tetraaza organic compounds, phosphoric and phosphonic acids, naphthenates, amidosulfonic acids, and amino acids. However, the pigments formed from these compounds provide only limited corrosion protection and do not approach the benefit derived from the use of hexavalent chromium.

In addition, the formation of manganese-containing pigments in which the manganese is complexed with ligands such as hydrazones, O bidentates, azomethines, phthalocyanines, azo and disazo complexes, N—S bidentates, oximes, tetraaza complexes, porphyrins, 1,2-dithiolates, and semicarbazones, has also been described. However, these compounds do not use tetravalent or trivalent manganese and are not used for anticorrosive applications.

U.S. Pat. No. 6,416,868 to Sullivan, et al. describes the use of alkaline earth-manganese oxides as pigments, wherein the alkaline earth is selected from Mg, Ca, Sr, and Ba. The pigments are described as being colorants and as resisting heat build-up due to infrared reflectance. Corrosion inhibiting characteristics of these compositions are not discussed or claimed. Additional manganese-containing colorants, frits, and ceramic pigments with no discussed or claimed anticorrosive properties are identified in U.S. Pat. No. 4,159,207 to Nuss, U.S. Pat. No. 3,832,205 to Lowery, and U.S. Pat. No. 5,254,162 to Speer, et al., and German Patent Nos. DE 4131 548 and DE 40 02 564, both to Speer, et al.

U.S. Pat. No. 4,469,521 to Salensky describes a corrosion-inhibiting pigment formed by sintering manganomanganic oxide (Mn ₃O₄) with oxides of calcium, zinc, barium, magnesium, or strontium.

U.S. Pat. No. 4,388,118 to Eppler describes a corrosion-inhibiting black pigment formed by calcining calcium or strontium oxides or carbonates with manganese oxides. The formed calcium manganese oxide or strontium manganese oxide pigments have very low oil absorption and high tint strength.

German Patents Nos. 26 42 049, 28 15 306, and 26 25 401 to Hund, et al. describe the use of calcined calcium/iron/aluminum/manganese oxides as corrosion-inhibiting pigments.

Manganese oxides themselves have been described as being constituents in corrosion-inhibiting formulations. For example, U.S. Pat. Nos. 4,417,007 and 4,417,008 to Salensky, et al. as well as Belgian Patent Nos. BE 893,677 to Chopra, et al. and BE 893,676 to Salensky, et al. describe manganomanganic oxide (Mn ₃O₄) as a constituent in a solvent-based paint formulation comprised of resin binders and additional extenders, fillers, and solvents. Manganese dioxide (MnO₂) is also described as an anticorrosive constituent within formulations in French Patent No. 2,348,257 to Zatmann and German Patent No. DE 39 35 478 to Ortlepp.

U.S. Pat. No. 4,788,411 to Skinner describes a paint composition described to prevent corrosion of welds. This composition is described as being composed primarily of zinc dust, with manganomanganic oxide (Mn ₃O₄) and organic binder included. The zinc pigment is described as being especially important for corrosion protection.

To date, no truly effective replacements have been developed for pigments based on CrVI or PbIV. Accordingly, the need remains for improved corrosion-protective pigments composed of currently unregulated and/or nontoxic materials which have an effectiveness, ease of application, and performance comparable to current CrVI or PbIV pigment formulations, and for methods of making and using the same.

SUMMARY OF THE INVENTION

This need is met by the present invention which represents a significant improvement in the formulation of non-toxic pigments through the use of trivalent or tetravalent manganese. Although the present invention is not limited to specific advantages or functionality, it is noted that the trivalent and/or tetravalent manganese pigments of the present invention have been demonstrated with accelerated corrosion testing to retard corrosion to a higher degree than prior art manganese pigments and other alternatives to CrVI- or PbIV-based corrosion inhibiting pigments. These pigments have been tested to inhibit corrosion to the same degree as zinc, strontium, and lead chromate-based CrVI pigments, as well as red lead or calcium plumbate Pb IV pigments. The raw materials are not exotic, are relatively inexpensive, and do not require complicated synthesis methods.

The present invention utilizes “valency stabilization” of the trivalent or tetravalent manganese ion in the as-formed pigments to achieve corrosion resistance comparable to the more soluble chromate-based CrVI pigments. More specifically, in order to achieve a high degree of corrosion resistance, a MnIII-based or MnIV-based pigment must exhibit the following characteristics:

1) A corrosion inhibiting pigment must contain a suitable source of oxidizing species. These species quickly oxidize bare metal and form a protective surface if bare metal is exposed in a coating breach.

2) A valence stabilizer for the trivalent or tetravalent manganese ion is necessary to ensure that the ion will not be reduced too quickly to the divalent state when released into solution or in the coating. The importance of stabilizing the manganese ion in its trivalent or tetravalent charge state was not previously recognized as critical to the corrosion inhibiting function of a pigment.

3) The MnIII or MnIV pigment powder must be a “sparingly soluble”, “low solubility”, or “insoluble” compound in water when dispersed in its binder-carrier system. If the pigment is too insoluble in a selected coating system that requires inhibitor release, an insufficient amount of corrosion inhibitor will be delivered to a flaw. A poorly formed, incomplete oxide layer produced by a pigment of too low solubility for a given binder-carrier system will not only fail to inhibit corrosion, but can promote crevice corrosion and result in locally enhanced corrosion rates.

The reservoir of oxidizing ions can be quickly flushed away if the pigment is too soluble, and typical corrosion will begin. Highly soluble pigments are also known to result in osmotic blistering of paint films and coatings. Trivalent or tetravalent manganese pigments that are too soluble can also be responsible for osmotic blistering depending on the aqueous permeability the carrier film.

It is difficult to place specific solubility values to these optimum “sparingly soluble”, “low solubility”, or “insoluble” pigment materials because there appear to be several variables associated with what makes an optimum anticorrosive pigment material (e.g., specific resin/binder system in which it is placed). The particle size and particle shape has been observed to noticeably affect the solubility of “low solubility” pigments such as lead chromate (e.g., May and Kolthoff, J. Phys. & Colloid Chem. 52: 836-54, 1948). The solubility of the candidate trivalent or tetravalent manganese pigment must be matched to the hexavalent chromium or tetravalent lead pigment that it is replacing (Table 1), such as zinc or strontium chromate, or calcium plumbate. If the trivalent or tetravalent manganese pigment exhibits a solubility in water of between about 1×10⁻⁴and about 1×10⁻¹moles per liter of trivalent or tetravalent manganese, then appreciable corrosion inhibition will be observed in the binder systems that typically incorporate zinc or strontium chromates (or calcium plumbate). Pigments that incorporate stabilized trivalent or tetravalent manganese compounds that fall outside of this particular range may also exhibit some corrosion inhibition as zinc or strontium chromate (or calcium plumbate) replacements. For example, pigments with solubilities as high as 1×10⁰moles per liter or as low as 1×10⁻⁵moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate zinc or strontium chromate (or lead plumbate), although not as great as those compounds which fall within the optimum solubility range. A solubility range from 1×10⁻⁶to 1×10⁻⁸moles per liter trivalent or tetravalent manganese is desirable for manganese pigments to inhibit corrosion in binder systems where lead chromate pigments are currently used. Pigments that incorporate trivalent or tetravalent manganese that fall slightly outside of this range may also inhibit corrosion as lead chromate replacements. For example, pigments with solubilities as high as 1×10⁻⁵moles per liter or as low as 1×10⁻⁹moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate lead chromate, although not as great as those compounds which fall within the optimum solubility range. Lastly, any trivalent or tetravalent manganese pigment that exhibits a solubility lower than 1×10⁻⁹, but higher than 1×10⁻¹⁷(based on red lead solubility) moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate red lead. Under special conditions (i.e., very carefully controlled particle sizes), trivalent or tetravalent manganese compounds with solubilities as high as 1×10⁻⁷moles per liter trivalent or tetravalent manganese can be used as red lead replacements. The solubility characteristics of the trivalent or tetravalent manganese in the pigment can be controlled through the use of valence stabilizer materials that form compounds that fall within the desired solubility ranges. A “controlled release” of trivalent or tetravalent manganese can thus be achieved similar to the “timed release” of hexavalent chromium or tetravalent lead in the “state-of-the-art” systems.

TABLE 1


Solubility Ranges for Trivalent and/or
Tetravalent Manganese Replacements for
Hexavalent Chromium or Tetravalent Lead Pigments

Hexavalent Chromium	Optimum Solubility	Acceptable Solubility
or Tetravalent Lead	Range (moles/L	Range (moles/L
Pigment to be Replaced	Mn⁺³and/or Mn⁺⁴)	Mn⁺³and/or Mn⁺⁴)

Zinc Chromates	1 × 10⁻¹(upper)	1 × 10⁰(upper)
(including basic forms)	to	to
Strontium Chromates	1 × 10⁻⁴(lower)	1 × 10⁻⁵(lower)
Calcium Plumbate
Lead Chromates	1 × 10⁻⁶(upper)	1 × 10⁻⁵(upper)
(including basic forms)	to	to
Lead Molybdate-Chromate	1 × 10⁻⁸(lower)	1 × 10⁻⁹(lower)
Lead Silicochromate
Red Lead	1 × 10⁻⁹(upper)	1 × 10⁻⁷(upper)
	to	to
	1 × 10⁻¹⁷(lower)	1 × 10⁻¹⁷(lower)

4) The “valence stabilizer” optionally helps establish an electrostatic barrier layer around the cation-stabilizer compound in aqueous solutions. The nature and character of the electrostatic double-layer surrounding the cation-stabilizer compound may be controlled and modified by careful selection of stabilizer species. In general, the electrostatic double layer formed acts to protect the cation from premature reaction with hydronium, hydroxide, and other ions in solution. The formation of electrostatic barrier layers also helps to impede the passage of corrosive ions through the binder phase to the metallic surface.

5) The trivalent or tetravalent manganese pigment material may also exhibit ion exchange behavior towards corrosion promoting ions, particularly alkali species. This optional consideration can be important because alkali ions are aggressive aqueous corrosion enhancers in alloys which contain metals such as aluminum, magnesium, or zinc.

6) The manganese/valence stabilizer complex can optionally exhibit a color change between the trivalent or tetravalent and divalent manganese oxidation states. This color change can act as a metric to determine when the “throwing power” associated with the pigments is no longer available, and when the paint system in which it is contained needs to be replaced. For this reason, it is also optionally important that the color of these pigments that exhibit a color change between divalent and trivalent or tetravalent oxidation states that is light-fast (i.e., not changed by strong light).

The effectiveness of an oxidizing species is a function of its individual oxidation-reduction potential, and more highly oxidized species exhibit greater corrosion protection, although lower stability. A stabilizer is necessary to provide a timed release of the inhibitor ion, as well as being needed to ensure that the oxidative strength will not be reduced too rapidly. Thus, a valence stabilizer is required for the trivalent or tetravalent manganese ion because of its reactivity and to produce controlled trivalent or tetravalent manganese solubilities. The corrosion resistance of a number of aluminum alloys as tested using both ASTM B-117 and ASTM G-85 has been enhanced through the use of stabilized trivalent and/or tetravalent manganese pigments. Not only do these optimized pigments retard corrosion to a higher degree than other prior art manganese pigments, but their corrosion resistance is comparable to that of hexavalent chromium or tetravalent lead systems.

In one aspect, the invention comprises a mechanistic and chemical approach to the production of corrosion-inhibiting pigments using trivalent or tetravalent manganese. This approach uses stabilizer materials which form compounds with trivalent or tetravalent manganese that match the observed solubilities of hexavalent chromium or tetravalent lead pigments currently in use (see Table 1). The solubility ranges reported provide a release of trivalent or tetravalent manganese at a rate slow enough that most binder systems will provide protection for an extended period of time and fast enough to inhibit corrosion during conventional accelerated corrosion testing methods such as ASTM B-117 and G-85. Compounds that fall slightly outside of the solubility ranges shown in Table 1 may also provide some corrosion-inhibiting activity under certain conditions and binder systems. However, pigment compounds with aqueous solubilities far outside of the target ranges are likely to be inefficient corrosion inhibitors. Solubility control can be achieved using organic or inorganic stabilizer materials.

In an optional aspect, the invention is the achievement of corrosion-resistant pigments using trivalent or tetravalent manganese by the use of stabilizer materials which form compounds that exhibit electrostatic dipoles to form electrostatic barrier layers composed of ions such as hydronium (H ₃O⁺) or hydroxide (OH⁻) in the presence of water. The formation of these electrostatic barrier layers through the use of stabilizer materials can be achieved using organic or inorganic materials.

In another optional aspect, the invention is the achievement of corrosion-resistant pigments using trivalent or tetravalent manganese by the use of stabilizer materials which form compounds that exhibit ion exchange behavior towards alkali ions. The formation of this ion exchange behavior can be achieved through the use of organic or inorganic materials.

In yet another optional aspect, the decomposition temperature of the trivalent or tetravalent manganese/valence stabilizer complex upon which the pigment is based should be above 100° C. In addition, the melting temperature of the complex is typically above 50° C., although lower-melting complexes may have some applications.

In still another optional aspect, the manganese/valence stabilizer complex upon which the pigment is based should exhibit a color change between the trivalent or tetravalent and divalent oxidation states. This allows for a visual metric of when the pigment has lost its “throwing power”, and the binder system within which it is contained must be replaced. Therefore, it is desirable that the color of these pigments be light-fast (unchanged by exposure to strong light).

These MnIII and MnIV compounds represent a substantial performance improvement over prior art related to pigment alternatives used to replace CrVI-based and PbIV-based corrosion inhibiting pigments. They also provide a capability to tailor the corrosion inhibiting pigment to the carrier system. This allows current binder/resin systems used for chromates or plumbates to be used for MnIII- or MnIV-based systems without modification. Likewise, new binder/carrier/resin systems with improved physical properties can be developed without the restriction of compatibility with zinc, strontium, or lead chromate; or plumbate pigments.

The raw materials needed for the solutions used to form these coatings are relatively inexpensive. The pigments do not use exotic materials or require complicated synthesis methods.

Accordingly, it is an object of the present invention to provide non-toxic, corrosion-protective pigments based on trivalent or tetravalent manganese and for methods of making and using the same. These and other objects and advantages of the present invention will be more fully understood from the following detailed description of the invention. It is noted that the scope of the claims is defined by the recitations therein and not by the specific discussion of features and advantages set forth in the present description.

DETAILED DESCRIPTION OF THE INVENTION

A. Starting Materials

Four general starting materials are used for the preparation of trivalent or tetravalent manganese corrosion-inhibiting pigments. These include a manganese source, an oxidation source (if the precursor is a divalent manganese salt), a valence stabilizer source, and optional additional solubility control agents.

1) Manganese Source

Manganese is a nontoxic, non-regulated replacement metal for chromium or lead that exhibits more than one oxidation state (MnII, MnIII, and MnIV). The oxidation reduction potential for MnIII-MnII is comparable to that of the CrVI-CrIII couple, and the oxidation-reduction potential for MnIV-MnIII is comparable to the PbIV-PbII couple. The ionic radii of MnIII (61 pm) and MnIV (54 pm) are slightly larger than the CrVI ion (44 pm), and they will have a correspondingly lower charge density (electrostatic field) per ion as compared to hexavalent chromium. Conversely, both MnIII and MnIV are smaller than PbIV (78 pm), and have a higher charge density (electrostatic field) per ion compared to tetravalent lead. These factors are important in the selection and design of trivalent or tetravalent manganese compounds that match or exceed the performance of hexavalent chromium or tetravalent lead pigments.

Unlike most other high valence metal (HVM) systems, trivalent and/or tetravalent manganese ions exhibit remarkable stability under many environmental conditions. The numerous examples of manganese minerals that contain MnIII or MnIV are evidence of this stability (see Table 2 below). Trivalent or tetravalent manganese-containing minerals could conceptually be used as corrosion-inhibiting pigments. (However, natural impurities contained therein would alter the compositions so that the pigment materials would exhibit altered solubility characteristics.) The trivalent or tetravalent manganese minerals shown in Table 2 could be used as precursors for the production of anticorrosive manganese pigments for lead chromate or red lead replacements.

TABLE 2


Naturally-Occurring Trivalent and/or Tetravalent
Manganese-Containing Minerals Useful as Feedstock
for Anticorrosive Manganese Pigment Production

		Manganese
	Approximate	Valence	Crystal
Mineral	Composition	State(s)	Structure

Pyrolusite	MnO₂	+4	Tetragonal
Hausmannite	Mn₃O₄	+3/+2	Tetragonal
Manganite	MnO(OH)	+3	Tetragonal
Ramsdellite	MnO₂	+4	Orthorhombic
Bixbyite	Mn₂O₃	+3	Cubic
Groutite	MnO(OH)	+3	Orthorhombic
Feitknechite	MnO(OH)	+3	Tetragonal
Akhtenskite	MnO₂	+4	Hexagonal
Buserite	MnO₂	+4	Unknown
Nsutite	Mn(O,OH)₂	+4/+3	Hexagonal
Hetacrolite	ZnMn₂O₄	+3	Tetragonal
Marokite	CaMn₂O₄	+3	Orthorhombic
Hydro-	HZnMn_2−xO₄	+3/+2	Tetragonal
hetaerolite
Braunite	Mn₇SiO₁₂	+3/+2	Tetragonal
Psilomelane	(Ba,H₂O)₂Mn₅O₁₀	+4/+3	Monoclinic
(aka Roman-
echite)
Crypt-	KMn₈O₁₆	+4/+3	Monoclinic or
omelane			Tetragonal
Manjiroite	(K,Na)Mn₈O₁₆	+4/+3	Tetragonal
Lithiophorite	(Al.Li)MnO₂(OH)₂	+4/+3	Hexagonal
Chal-	(Zn,Fe,Mn)Mn₃O₇	+4	Rhombohedral
cophanite
Hollandite	(Ba,K,Na)Mn₈(O,OH)₁₆	+4/+3	Unknown
Woodruffite	(Zn,Mn)Mn₃O₇	+4	Tetragonal
Neltnerite	CaMn₆SiO₁₂	+3	Tetragonal
Birnessite	Na₄Mn₁₄O₂₇	+4/+3	Hexagonal
Asbolane	(Ni,Co)_xMn(O,OH)₄	+4/+3	Hexagonal
Todorokite	(K,Ca,Na)(Mn,Al,Mg)₆O₁₂	+4/+3	Monoclinic
Vernadite	(Mn,Fe,Ca,Na)(O,OH)₂	+4/+3	Hexagonal

a) Manganese Sources for “Sparingly Soluble” Pigments

Zinc and strontium chromates, as well as calcium plumbate, are “sparingly soluble” in water, and are typically formed via precipitation from a liquid media (i.e., water), with subsequent particle sizing and powder processing. Trivalent or tetravalent manganese pigments to be used for the same applications as zinc and strontium chromates, or calcium plumbate, are produced in a similar fashion. This is because the higher solubility requirements (1×10 ⁻¹to 1×10⁻⁴moles/liter inhibitor ion) for these pigments necessitate much higher release rates of MnIII or MnIV than can typically be achieved by calcined or “fired” materials. MnIII or MnIV compounds that can achieve high solubilities and release rates require special valence stabilizer and/or solubility control agents. The easiest preparative method for these constituents is via precipitation processes.

Manganese precursors for “sparingly soluble” pigments can be nearly any water, alcohol, or hydrocarbon soluble manganese compound in which the manganese is in the divalent, trivalent, tetravalent, or heptavalent oxidation state. Water-soluble precursors are typically used. Inorganic divalent manganese precursor compounds include, but are not limited to, manganese nitrate, manganese sulfate, manganese perchlorate, manganese chloride, manganese fluoride, manganese bromide, manganese iodide, manganese bromate, manganese chlorate, and complex fluorides such as manganese fluosilicate, manganese fluotitanate, manganese fluozirconate, manganese fluoborate, and manganese fluoaluminate. Organometallic divalent manganese precursor compounds include, but are not limited to, manganese formate, manganese acetate, manganese propionate, manganese butyrate, manganese valerate, manganese benzoate, manganese glycolate, manganese lactate, manganese tartronate, manganese malate, manganese tartrate, manganese citrate, manganese benzenesulfonate, manganese thiocyanate, and manganese acetylacetonate.

The manganese precursor for “sparingly soluble” pigments may also be a compound with manganese already in the trivalent or tetravalent oxidation state. A representative example is manganese III acetylacetonate. The manganese precursor for “sparingly soluble” pigments may be a compound with the manganese in the heptavalent oxidation state (permanganates). Heptavalent manganese precursors include, but are not limited to: potassium permanganate, sodium permanganate, lithium permanganate, ammonium permanganate, magnesium permanganate, calcium permanganate, strontium permanganate, barium permanganate, zinc permanganate, ferric permanganate, nickel permanganate, copper permanganate, cobalt permanganate, cerium permanganate, lanthanum permanganate, yttrium permanganate, and aluminum permanganate.

b) Manganese Sources for “Low Solubility” or “Insoluble” Pigments

Lead chromates are typically formed via precipitation from aqueous solution, while red lead pigments are produced by firing PbII oxide (PbO) in an oxidizing environment at approximately 400° C. Trivalent or tetravalent manganese compounds to be used as lead chromate or red lead replacements can be formed in two ways: 1) precipitating a manganese compound from a liquid medium and then firing or calcining the resultant precipitate; or 2) calcining or firing a manganese-containing compound or mixture using insoluble precursors. The commonality between these two options is firing, calcining, or otherwise heating a manganese-containing compound or mixture. The only manganese compounds suitable as replacements for lead chromate or red lead pigments (<1×10 ⁻⁵moles/liter inhibitor ion) are those produced by calcining or heating manganese compounds with or without other additives.

Soluble manganese sources for precipitation prior to calcining, firing, or otherwise heating are similar to those described above for “sparingly soluble” pigments. Insoluble manganese-containing compounds useful as precursors include MnII, MnIII, MnIV, and some MnIV compounds. Insoluble divalent manganese compounds useful as precursors include, but are not limited to: manganese oxide (manganosite), manganese hydroxide (pyrochroite), manganese carbonate (rhodochrosite), manganese silicate (rhodonite, tephroite, manganhumite, or manganjustite), manganese sulfide (alabandite or hauerite), manganese phosphate (reddingite or hureaulite), manganese oxalate, and manganese borate. Insoluble trivalent manganese or tetravalent manganese compounds suitable as precursors include manganese dioxide (MnO ₂), manganomanganic oxide (Mn₃O₄), manganese sesquioxide (Mn₂O₃), lithiated manganese spinel (LiMn₂O₄), and manganese III hydroxide (MnOOH). The MnIII and MnIV containing minerals described in Table 1 are also useful insoluble trivalent and tetravalent manganese precursors.

MnIII and MnIV are capable of providing corrosion protection at a distance to a metal surface in the presence of coating flaws such as scrapes, scratches, and holes because of their throwing power. The solubility of the MnIII or MnIV compound needs to be tailored to suit the needs of the protection system and must be neither too high, nor too low in that system. The protective system includes the binder phase, assorted modifiers, and under- and over-coatings. The system needs to be performance matched to its intended usage environment. Timely release and throwing power of the inhibitor are critical to protective performance, but controlled tailoring of these has not been taught in prior art. Likewise, the body of systematic chemistry data required to control these properties has not been readily available in a form useful to help design coatings. The present invention outlines how to stabilize MnIII and MnIV with a variety of materials so the MnIII and MnIV may be adapted to a multitude of pigment applications with specific compatibility requirements.

2) Oxidation Source

If MnIII and/or MnIV pigment compounds are produced via precipitation, an oxidizing species will typically be included in the synthesis solution if divalent manganese compounds are used as precursors for MnIII and MnIV. Otherwise, a post-precipitation oxidation step will be required. Additional amounts of oxidizer may be added to help control and maintain a desired amount of MnIII/MnIV in the pigment solution by reoxidizing MnIII/MnIV that has become reduced. The trivalent manganese ion is an exceptionally good oxidizing species with an oxidation-reduction potential of +1.49 V at a pH of 0 for the MnIII-MnII couple in water, and the tetravalent manganese ion is an even stronger oxidizing species, with a redox potential of +1.65 V under similar conditions. Strong oxidizers are required because of the high potential of their redox reaction. The oxidizers may be gases, liquids, or solids. Solid oxidizers are typically used for this application due to ease of handling and reagent measurement. Other starting materials (manganese source and stabilizer source) will also frequently be solids. Liquid oxidizers may be used, but handling and accurate process metering have proven difficult. Gaseous oxidizers may be the most cost effective and chemically efficient on a large scale, but are also the most problematic due to handling and venting concerns.

Oxidizers suited for the purpose of producing and maintaining the manganese ion in the trivalent or tetravalent charge state include but are not restricted to peroxides and peroxo compounds (including superoxides, persulfates, perborates, pernitrates, perphosphates, percarbonates, persilicates, peraluminates, pertitanates, perzirconates, permolybdates, pertungstates, pervanadates, and organic peroxyacid derivatives), ozone, hypochlorites, chlorates, perchlorates, nitrates, nitrites, vanadates, iodates, hypobromites, chlorites, bromates, permanganates, periodates, and dissolved gases such as oxygen, fluorine, or chlorine. Inorganic and organic derivatives of these compounds may be used. Typical oxidizers for this use are peroxides, persulfates, perbenzoates, periodates, bromates, hypochlorites, gaseous dissolved oxygen, and even the oxygen content of air. In general, any inorganic, organic, or combination species with an oxidation potential of +1.0 V or greater (at a pH of 1) will be capable of oxidizing divalent manganese to the trivalent or tetravalent oxidation state.

Oxidized manganese may also be produced in solution by electrolytic oxidation. However, this approach may not be economically feasible due to the energy costs associated with electrolytic oxidation. Chemical oxidation, such as that described above, currently offers the best-value approach for oxidizing manganese to the trivalent or tetravalent state.

It is also possible to produce a divalent manganese/valence stabilizer complex, and then apply an oxidizer to oxidize divalent manganese to trivalent or tetravalent manganese. This, however, is less typical because the percentage of trivalent or tetravalent manganese will decrease from the outside to the interior of the pigment particle.

Oxygen (including the oxygen content of air) is the most useful oxidizer source for the production of “low solubility” or “insoluble” trivalent or tetravalent manganese pigment compounds via calcining, firing, or otherwise heating processes. The control of temperature, partial pressure of oxygen, flowrate, and even particle size allows the oxidation state of the manganese in the sintered particle to be divalent, trivalent, or tetravalent. Other oxidizing gasses such as NO _x, SO_x, chlorine, fluorine, or ozone can also be used, but these are less desirable due to their environmental impact.

3) Valence Stabilizers

Manganese is effective as an oxidative corrosion inhibitor if it can be supplied in sufficient quantities in the trivalent and/or tetravalent charge-state when brought into contact with unprotected bare metal. Corrosion resistance comparable to that of CrVI or PbIV can be achieved by the use of MnIII and/or MnIV oxidizer ions in pigment compounds. Valence stabilizers are materials that, when assembled, modify the rate of reduction and the solubility of the MnIII and/or MnIV ions. Valence stabilization has not been previously recognized as an important consideration in the development of effective corrosion inhibiting pigments. Stabilization helps avoid reduction and premature conversion of the ion to the divalent charge-state during compound formation, carrier incorporation, application, and exposure to a corrosive environment. Stabilizers control solubility, mobility, ion exchange, binder compatibility, and the degree of surface wetting. The exact solubility of this compound may be modified by species released into solution by the dissolving metal surface or by the subsequent addition of solubility control agents. A variety of inorganic and organic stabilizers are available that can serve to control solubility. The stabilizer may also act as an ion-exchange host and/or trap for alkali or halide ions in solution.

Valence stabilization is necessary for MnIII and MnIV due to the reactivity of these ions with water. Unlike MnII, which can readily be solubilized in water, MnIII and MnIV ions rapidly react with water, producing elemental oxygen. Valence stabilization is particularly useful for the more soluble MnIII and MnIV compounds (i.e., >1×10 ⁻⁵moles/liter of inhibitor ion) where more rapid release rates of these ions are necessary. For example, manganese dioxide (MnO₂) is reported to exhibit a solubility in water between 2.4×10⁻⁵and 4.0×10⁻⁷moles/liter Mn⁺⁴, depending upon pH (Swain, et al., Anal. Chem. 47(7): 1135-7, 1975 and Savenko, Geokhimiya (3) pp. 416-9, 1985). Similarly, manganese sesquioxide (Mn₂O₃) is reported to exhibit a solubility in water between 3.3×10⁻⁸and 5.1×10⁻⁹moles/liter Mn⁺³, depending upon temperature (Ampelogova, et al., Radiokhimiya 31(4): 160-5, 1989). For these low solubility compounds, oxygen (O) is a satisfactory “valence stabilizer” to achieve the desired solubilities and release rates. Specialized valence stabilizers are necessary for MnIII and MnIV compounds of solubilities higher than 1×10⁻⁵moles/liter Mn⁺³or Mn⁺⁴.

The need for “valence stabilization” of trivalent or tetravalent manganese for corrosion inhibition has only been indirectly noted in the general corrosion literature as a synergistic enhancement. Corrosion inhibition behavior of nitrogen-containing organics such as aniline or pyridine has been reported to be enhanced with the addition of manganese. The exact nature of this “synergistic enhancement” has never been adequately explained. These “synergistic” mixtures of nitrogen-containing organics and manganese have also been described as being “oxygen-scavengers”, and the organics are frequently observed to “chemisorb” onto the substrate piece being protected.

This enhancement can be explained by the “valence stabilization” model of corrosion inhibition by trivalent or tetravalent manganese outlined here. Nitrogen-containing organics and manganese result in the formation of an organometallic complex where the central manganese ion can be stabilized in a higher oxidation state. The observed “oxygen-scavenging” phenomenon associated with dissolved oxygen in aqueous solutions is easily explained by the oxidation of stabilized divalent manganese to the trivalent or tetravalent state. “Sparingly soluble” MnIII or MnIV complexes containing these organics are responsible for the corrosion inhibiting activity, and these organics will appear to be “adsorbed” or “chemisorbed” from solution onto the metal piece being protected due to precipitation.

The key to providing a useful source of trivalent or tetravalent manganese at a metal surface is the creation of a compound in which the MnIII or MnIV ion is shielded from premature reduction during and after pigment formation. The formation of pigments with the proper release rate of MnIII or MnIV ions is problematic because of the instability of MnIII and MnIV in solution. A valence stabilizer must assemble around MnIII or MnIV to form a compound in order to produce the active corrosion-inhibiting component in a pigment. It is difficult to place specific solubility values to these optimum sparingly soluble pigments because of the wide range of binder systems in which corrosion-inhibiting pigments are used.

In order to replace the zinc chromates, strontium chromate, or calcium plumbate pigments, a MnIII- or MnIV-stabilized compound with a solubility in water of between about 1×10 ⁻⁴and about 1×10⁻¹moles per liter of trivalent or tetravalent manganese should exhibit appreciable corrosion inhibition when used as a primer pigment. This solubility range provides a release of trivalent or tetravalent manganese at a rate slow enough that protection will be provided for an extended period of time and fast enough to inhibit corrosion during conventional accelerated corrosion testing methods such as ASTM B-117 and G-85 for coatings that contain these pigments. Manganese compounds that fall outside of this particular solubility range may exhibit a small degree of corrosion inhibition in the binder systems that currently use the zinc or strontium chromate pigments. For example, compositions with solubilities as high as 1×10⁰moles per liter or as low as 1×10⁻⁵moles per liter of trivalent or tetravalent manganese will exhibit some corrosion resistance, although they will not be as effective as those compounds within the optimum solubility range. A common MnIII compound (MnIII acetylacetonate) is too soluble to provide effective corrosion inhibition if incorporated into a binder system such as a paint. Other compounds, such as Mn₃O₄as described in the prior art, will not serve as effective corrosion inhibiting pigments in the binder systems that currently use the zinc or strontium chromate pigments because they are too insoluble.

The needed solubility will be strongly dependent on the net aqueous solubility of overlying paints and coatings and their usage environment. For example, solubility tailoring would be useful in a situation where a protected substrate is suddenly immersed in seawater, or where a rubber sealant allows only limited water penetration. Adequate corrosion protection could be achieved through the formation of a trivalent or tetravalent manganese pigment compound that exhibits a higher solubility in water (e.g., 1×10 ⁰to 1×10⁻³moles per liter MnIII or MnIV). A rapid release of protective trivalent or tetravalent manganese ions would happen at the expense of depleting the manganese quickly from the coating. Trivalent or tetravalent manganese pigments of lower solubilities (e.g., 5×10⁻⁵to 1×10⁻³moles per liter MnIII or MnIV) may also be useful in some situations (e.g., as paints in nearly pure deoxygenated water). The number and range of compound solubilities offered by valence stabilized MnIII and MnIV compounds allows the development of protective coating systems with broad performance and application ranges. This feature is not presently available even for CrVI based corrosion inhibiting pigments.

Any material in the synthesis bath which complexes with trivalent or tetravalent manganese (whether inorganic or organic) and which results in the formation of a MnIII- or MnIV-containing compound that exhibits solubilities within or near this solubility range can serve as a valence stabilizer for trivalent or tetravalent manganese. The assembly of a protective shell around the highly charged MnIII or MnIV and its associated oxygen and hydroxyl species can help control the rate at which the manganese is reduced and its oxygen is released. Proper selection of materials for forming the protective shell will allow solubility tailoring of the entire assembly to its intended application environment. Valence stabilizers described above may need some type of additional solubility control to optimize the performance of the trivalent or tetravalent manganese-valence stabilizer compound. Additional solubility control agents may be in the form of inorganic or organic compounds. Their use is optional rather than a requirement for effective valence stabilization and solubility control.

Trivalent or tetravalent manganese-containing compounds that are useful as replacements for lead chromate or red lead pigments require lower solubilities. A typical formula for a red lead paint is:



	Red lead (Pb₃O₄)	80 wt. Percent
	Linseed oil	18 wt. Percent
	Turpentine and liquid drier	2 wt. Percent

The majority of this paint system is pigment. If the pigment in this paint system exhibited excessive solubilities for this specific application, the coating would quickly be exhausted, leaving limited protection for the underlying metal.

An optimum solubility range from 1×10 ⁻⁶to 1×10⁻⁸moles per liter trivalent or tetravalent manganese is desirable for manganese pigments to inhibit corrosion in the binder systems that lead chromate pigments currently are used in. Pigments that incorporate trivalent or tetravalent manganese that fall slightly outside of this range may also inhibit corrosion as lead chromate replacements. For example, pigments with solubilities as high as 1×10⁻⁵moles per liter or as low as 1×10⁻⁹moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate lead chromate, although not as great as those compounds which fall within the optimum solubility range.

Any trivalent or tetravalent manganese pigment that exhibits a solubility lower than 1×10 ⁻⁹moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate red lead. Under special conditions (i.e., very carefully controlled particle sizes), trivalent or tetravalent manganese compounds with solubilities as high as 1×10⁻⁷moles per liter trivalent or tetravalent manganese can be used as red lead replacements.

As with the more soluble MnIII and MnIV compounds used as zinc or strontium chromate replacements, changes in pigment solubility can be achieved through the use of additional solubility control agents.

Several variables are associated with making optimized pigments. If the pigment is too insoluble for the specific application, then insufficient trivalent or tetravalent manganese is available to inhibit corrosion. Low solubility compounds that do not provide a sufficient amount of oxidation quickly enough to a coating breach may produce an incomplete oxide layer and thus an ineffective barrier film. If the manganese pigment is too soluble, it will be washed away quickly, and an incomplete thin oxide film will form that will not provide long-term corrosion protection, or osmotic blistering of the paint system may result. The formation of spotty or patchy oxides can promote localized crevice corrosion and can result in enhanced corrosion rates at the breach.

The traditional chromate pigments are used not only in alkyd resin systems (e.g., DoD-P-15328D Wash Primers), but also in acrylic systems (e.g., MIL-P-28577B Water-Borne Acrylic Primers), and even in sulfonated rubber sealants (e.g., MIL-PRF-81733D Sealing and Coating Compound). Tetravalent lead pigments are typically used in either oil-based (i.e., linseed oil) paint systems, although some are used in alkyd resin coatings. Fortunately, it is possible to tailor the MnIII and/or MnIV valence stabilizer compound pigment systems themselves to specific binder/solvent systems using solubility (cohesion) parameters. Solubility parameters define how well an inorganic or organometallic complex will disperse in a given resin/binder system. This represents a radical departure from traditional paint systems, in which the paint systems are configured to specific pigments.

The formation of an electrostatic double layer can be important for the effectiveness of a corrosion inhibitor once it is released into solution during corrosion. There are differences in anodic and cathodic polarization, solubility, and the saturated pH of aqueous solutions of various chromate or plumbate pigments. The formation of an electrostatic double layer around the pigment while in its carrier film will not be as important as when the species is in solution. For this reason, the development of an electrostatic double layer around the pigment is an optional consideration. For example, zinc chromate pigment-filled paint does not exhibit electrochemical inhibiting behavior. The carrier film typically behaves as a water impermeable barrier and will muffle the polar character of the pigment. The hexavalent chromium pigments SrCrO ₄and ZnCrO₄have very small barrier layers associated with them, but they are effective as corrosion-inhibiting pigments. Optimized solubility for MnIII- or MnIV-valence stabilizer compounds alone can result in corrosion resistance comparable to the state-of-the-art chromium pigments. The degree of polarization exhibited by the MnIII or MnIV ions will be less than the CrVI ion because of their larger ionic radius and lower charge-state, and they will not be as efficient in forming electrostatic double layers in aqueous solution. The valence stabilization of trivalent or tetravalent manganese should be optimized to achieve the highest degree of efficiency in both solubility control and polar character, in order to further enhance the corrosion resistance.

Conversely, because both the MnIII and MnIV ions are smaller than the PbIV ion, the degree of polarization exhibited by these ions will be greater than PbIV, and they will be more effective in forming electrostatic double layers in aqueous solution. In order to replace PbIV pigments, a lower degree of valence stabilization is therefore acceptable.

The nature and character of the “electrostatic double layer” surrounding the trivalent or tetravalent manganese/valence stabilizer compound may be controlled and modified by careful selection of organic or inorganic stabilizers. Characteristics such as the electrical dipole moment and the shape/conformation (for steric effects) of the stabilizer were found to influence the performance of the corrosion-inhibiting pigment. These stabilizer ions establish a protective electrostatic shell around the cation-stabilizer compound and gather additional layers of ions such as hydronium (H ₃O⁺) or hydroxide (OH⁻) about them. The size of the electrostatic double layer is a function of the electrostatic potential at the compound surface and is inversely proportional to the ionic strength of the surrounding solution. An electrostatic double layer will likely form in aqueous solution for compounds that can carry a charge, have a natural electrostatic dipole, or can have an induced dipole. However, these compounds do not normally act as corrosion inhibitors because they have not been optimized for that purpose.

The melting point and decomposition temperature of the pigment material are important. Trivalent or tetravalent manganese-valence stabilizer compounds that decompose below about 100° C. limit both their useful lifetimes and range of use. The melting temperature should be above about 50° C. to ensure that the liquid phase does not form during normal handling procedures. An additive may be needed for pigments with melting temperatures below about 50° C. Inert solid addendum materials need not have any inherent corrosion-inhibiting capability and are used to provide a base (support) that the pigment can absorb on or into. Oxides, phosphates, borates, silicates, and polymers are examples of support compounds that can be used. Low melting temperature pigments (below about 50° C.) can be used, but they require handling and processing different from higher melting temperature pigments. Liquid-phase corrosion inhibitors based on MnIII, MnIV, and CrVI pigments have been demonstrated to provide excellent performance as corrosion inhibitors in primer paint systems.

The corrosion-inhibiting pigments of the present invention can optionally exhibit a color change between oxidized species and divalent species. The implications of these color changes from an applications standpoint are significant. Color changes in the pigment material in use can be used as a metric to determine when the pigment no longer exhibits corrosion-inhibiting action as a result of depleting the oxidized ion. Changes in hue of the pigment can be used to determine how much service life remains for that pigment in terms of corrosion-inhibiting capacity. Valence based color change is an attribute that conventional chromate or plumbate pigments do not exhibit. The color change associated with their redox reaction of chromate or plumbate pigments is insignificant as the pigments are reduced and “depleted” of their corrosion-inhibitive capability. Thus, trivalent or tetravalent manganese/valence stabilizer combinations that exhibit these color changes are superior to chromium or lead in terms of providing an easily measured, easily observed metric to gauge remaining service life of the pigment. However, this color change should not be initiated by exposure to strong light. Light-fast pigments are therefore desirable for these indicator pigments.

The incorporation of the valence stabilizer (inorganic or organic) may optionally result in the formation of a MnIII- or MnIV-valence stabilizer compound that also exhibits ion exchange behavior towards alkali ions. This is not a requirement of the MnIII- or MnIV-valence stabilizer compound, and pigments that do not exhibit this phenomenon have been successfully demonstrated to inhibit corrosive attack. However, it is a desirable characteristic for enhanced corrosion resistance. Existing CrVI-based or PbIV-based pigment systems do not exhibit this behavior to any significant degree.

The design of suitable MnIII- or MnIV-valence stabilizer compounds allows typical and less typical stabilizers to be identified. The general classes of compounds described below represent only a first approximation of whether a specific coordination compound will provide favorable or unfavorable properties in a MnIII- or MnIV-valence stabilizer compound. Property tailoring can also take place through selection of specific anions or cations bound to the MnIII- or MnIV-valence stabilizer coordination compound. The “physiology” of inorganic stabilizers is simple because of the limited number of atoms and structural arrangements involved in their formation. The “physiology” of organic stabilizers is not as simple. An organically stabilized manganese compound may have one or more organic ligands that may have one or more bonding sites that can interact with the MnIII or MnIV ion/oxide cluster. The bonding groups can be the same or different atoms or functional groups on an individual or a variety of ligands. An organic stabilizer ligand can be modified in an unlimited number of ways to tailor its physical behavior with respect to such properties as chemical reactivity, solubility, electrostatic and polar character, and functional behavior.

It is possible to fine tune the electronic and structural characteristics of a MnIII- or MnIV-valence stabilizer compound further via substituent groups on the coordinating ligand, and/or by the selection of cations or anions to complete the charge balance of the MnIII- or MnIV-valence stabilizer compound. For example, some substituent groups have large dipole moments associated with them, which will increase the electrostatic barrier layers associated with the manganese/valence stabilizer complexes. These include: ketones (═C═O), thioketones (═C═S), amides (—C[═O]—NR ₂), thioamides (—C[═S]—NR₂), nitrites or cyano groups, (—CN), isocyanides (—NC), nitroso groups (—N═O), thionitroso groups (—N═S), nitro groups (—NO₂), azido groups (—N₃), cyanamide or cyanonitrene groups (═N—CN), cyanate groups (—O—CN), isocyanate groups (—N—C═O), thiocyanate groups (—S—CN), isothiocyanate groups (—N═C═S), nitrosamine groups (═N—N═O), thionitrosamine groups (═N—N═S), nitramine groups (═N—NO₂), thionitramine groups (═N—NS₂), carbonylnitrene groups (—CO—N), thiocarbonylnitrene groups (—CS—N), sulfenyl halides (—S—X), sulfoxides (—S═O), sulfones (═S[═O]₂), sulfinyl groups (—N═S═O), thiosulfinyl groups (—N═S=S), sulfenyl thiocyanato groups (—S—S—CN), sulfenyl cyanato groups (—S—O—CN), sulfodiimine groups (═S[═NH]₂), sulfur dihaloimido groups (—N═SX₂), sulfur oxide dihaloimido groups (—N═S[═O]X₂), aminosulfur oxide trihalide groups (═N—S[═O]X₃), sulfonyl azide groups (—S[═O]₂N₃), sulfonyl thiocyanate groups (—S[═O]₂SCN), sulfonyl cyanate groups (—S[═O]₂OCN), sulfonyl cyanide groups (—S [═O]₂CN), halosulfonate groups (—S[═O]₂OX), phosphonyl thiocyanate groups (—P[═O]OHSCN), phosphonyl cyanate groups (—P[═O]OHOCN), and phosphonyl cyanide groups (—P[═O]OHCN). In this way, the characteristics of less typical coordinating ligands may be adjusted so that the resultant MnIII- or MnIV-valence stabilizer compound does exhibit some degree of corrosion inhibition. Conversely, the physical characteristics of typical coordination compounds can be adjusted so that they are no longer suitable as a corrosion inhibitor.

Valence stabilizers can be either organic or inorganic compounds. Manganese coordination chemistry, which has been the subject of numerous scientific studies for almost 100 years, identifies chemical binding preferences, structure stability, and the physical properties of the resulting compounds. Producing effective MnIII- and/or MnIV-valence stabilizer compounds requires understanding the electrostatic and structural influence of candidate species on the compound. The solubility of the valence stabilized MnIII- and/or MnIV-compound scales roughly with the inverse of its diameter. The MnIII and MnIV ions and their layer of negatively charged hydroxyl ions are very small, which results in a high degree of aqueous solubility. The field strength of the complex also scales with the inverse of its physical diameter. Large compounds with an optimal degree of solubility will not necessarily be ideal with respect to the size of their electrostatic double layer. The size of the ligand must therefore be balanced against the desired electrical properties. The MnIII ion generally favors complexation either in the square pyramidal (coordination number 5) or octahedral (coordination number 6) arrangements, although it will occasionally be found in a pentagonal bipyramid arrangement. The MnIV ion almost exclusively favors complexation in the octahedral (coordination number 6) arrangement. Valence stabilizers (and stabilizer combinations) should be selected with the goal of achieving these coordinations.

Stabilizers can be designed that result in manganese compounds with the necessary physical, electrical, and chemical properties to perform as corrosion inhibitors with this information. The nature of a particular valence stabilizer shell surrounding the manganese ion, or combination of valence stabilizers, can be further manipulated by the selection of appropriate “shaping groups” and heteroatoms at the binding site. Inorganic valence stabilizers are typically oxygen-containing coordinations. Therefore, manipulation of different sized ionic complexes around the MnIII or MnIV ions is best controlled through adjustment of the heteroatoms (e.g., Mo, W, Te, etc.) within these “polymerized” oxygen-containing ionic complexes (ligands).

For organic compounds, the physical geometry of the binding sites is important to the stability of the MnIII- or MnIV-stabilizer compound. The influence of site geometry becomes evident when the solvation shell of a MnIII or MnIV ion is replaced by the ligand donor atoms as when pigments are formed. The number of available ligand binding sites should be at least equal to the standard coordination number of the MnIII or MnIV ion. The balance between solvation of the ligand and MnIII and/or MnIV and their complexation where MnIII or MnIV is solvated by a specific ligand is critical in maintaining stability. MnIII- or MnIV-ligand attraction increases with the number of available binding sites on the ligand. However, with an increasing number of binding sites, site-site repulsions will also increase, resulting in lower stability.

The number of binding sites available on the complexing ligand is important to the resulting MnIII- or MnIV-stabilizer's properties. Several ligands are required to effectively stabilize MnIII or MnIV if the chosen ligand has only one binding site. For example, six NH ₃ligands are needed to octahedrally coordinate MnIII in a hexaaminemanganese(III) compound because NH₃has only one binding site. Bulky ligands with only one binding site, like pyridine, can be sterically hindered from packing tightly around the ion and will result in decreased compound stability. Conversely, macrocyclic organic and polymeric inorganic ligands can have many suitable binding sites. However, instability will result if a MnIII or MnIV ion is not completely embraced by all of the multiple macromolecular bonding sites on the ligand. For example, if a macromolecule surrounding the MnIII or MnIV ion has an insufficient number of binding sites available for charge balance, then the MnIII- or MnIV-stabilizer compound will be much less stable than a macromolecule that contains an adequate number of sites.

The stability of the MnIII- or MnIV-organic compound is strongly influenced by the charge, charge sign, and degree of polarizability of specific binding sites. Factors influencing compound stability include: 1) ion-pair interactions for charged ligands and MnIII or MnIV; 2) ion-dipole and ion-induced dipole interactions for neutral ligands; 3) hydrogen bonding; and 4) the hard-soft acid-base (HSAB) rules convention of coordination chemistry. HSAB rules help identify functional groups on ligands that might be effective as binding sites. Optimum binding for organic valence stabilizers to MnIII or MnIV will be with ligands with hard bonding species such as those that contain oxygen or nitrogen. Certain coordination complexes of the soft base sulfur are also effective for binding with MnIII or MnIV. HSAB rules can also help identify groups that might provide a degree of polarization to the stabilizer because of their large dipole moments. The nature-of bonding-between the MnIII or MnIV ion/oxide cluster and the stabilizer ligand can be altered by using a substituent group to modify the stabilizer. Specific interactions between the ligand and MnIII or MnIV can be tailored by substituent group selection coupled with altering the size or geometry of the complexing ligand. Some substituent groups, such as carbonyls (ketones, amides, ureas), nitro groups, cyano groups, and azido groups have large dipole moments. The polarization of the MnIII- or MnIV-stabilizer can therefore be optimized via evaluation of the effect of ligand type and substituents.

Finally, the size of the valence stabilizer plays an important role in solubility control of the resultant MnIII- or MnIV-valence stabilizer compound. As the ligand increases in size, it becomes more difficult to keep it in solution, therefore lowering the solubility. However, this must be balanced against the fact that as ligands are increased in size, it also becomes more difficult to establish the necessary dipoles at the compound/water interface. The size of the ligand must therefore be balanced against the desired electrical properties. The addition (or subtraction) of functional groups on organic valence stabilizers can be used to modify the solubility of the formed Mn ⁺³or Mn⁺⁴/valence stabilizer species. For example, the addition of sulfonated groups (—SO₃ ⁻) to organic valence stabilizers will significantly increase the solubility in water. Other substituent groups that will increase the solubility in water include: carboxyl groups (—CO₂—), hydroxyl groups (—OH), ester groups (—CO₃—), carbonyl groups (═C═O), amine groups (—NH₂), nitrosamine groups (═N—N═O), carbonylnitrene groups (—CO—N), sulfoxide groups (═S═O), sulfone groups (═S[═O]₂), sulfinyl groups (—N═S═O), sulfodiimines (═S[═NH]₂), sulfonyl halide groups (—S[═O]₂X), sulfonamide groups (—S[═O]₂NH₂), monohalosulfonamide groups (—S[═O]₂NHX), dihalosulfonamide groups (—S[═O]₂MX₂), halosulfonate groups (—S[═O]₂OX), halosulfonate amide groups (═N—S[═O]₂X), aminosulfonate groups (═N—S[═O]₂OH), iminodisulfonate groups (—N[SO₃ ⁻]₂), phosphonate groups (—PO₃ ⁻²), phospbonamide groups (—PO₂NH₂ ⁻), phosphondiamide groups (—PO[NH₂]₂), aminophosphonate groups (—N—PO₃ ⁻²), and iminodiphosphonate groups (—N[PO₃ ^−2] ₂). Conversely, the addition of nitro groups (—NO₂), perfluoroalkyl groups (—C_xF_2x+1), perchloroalkyl groups (—C_xCl_2x+1), nitramine groups (—N—NO₂), thioketone groups (═C═S), sulfenyl halide groups (—S—X), and sulfur dibaloimide groups (—N═SX₂) to organic valence stabilizers will decrease the solubility in water. In this way, the solubility characteristics of valence stabilizers can be “tailored” to meet specific binder/resin needs.

Valence stabilizers-and combinations of stabilizers can be manipulated by the selection of “shaping groups” and heteroatoms positioned at the binding site. Saturated organic chains can form flexible ligands that wrap around MnIII- or MnIV- and can enhance their stability. Unsaturated organics typically have less freedom to bend and contort and are less likely to be a ligand that can wrap or fit around the MnIII or MnIV ions. Addition of substituents onto an organic ligand may further restrict its freedom to flex. For example, the attachment of a phenyl group onto an organic valence stabilizer that contains two or more binding sites will likely restrict the ability of that ligand to flex around the MnIII or MnIV ions so as to coordinate it as a square pyramid or octahedral complex.

The physical, chemical, and electrostatic requirements for the design of effective pigments based on MnIII- or MnIV-stabilizer compounds result in lists of stabilizers that may be divided into wide band or narrow band stabilizer classes for MnIII or MnIV, depending upon the application. Wide band valence stabilizers can be used under a wide variety of service conditions (e.g., corroding specie, temperature, etc.) to achieve a high degree of corrosion resistance. Wide band physical properties (stability, solubility, and polarization) can be achieved by both inorganic or organic valence stabilizers. The desirable physical property of ion exchange can also be achieved with both inorganic and organic coordination compounds. “Narrow band” valence stabilizers result in satisfactory pigments only under limited applications. Table 3 lists the wide and narrow band valence stabilizers for MnIII and MnIV depending upon the specific application.

The compounds listed here are general guides for the initial selection of a coordination compound and do not represent a complete list. Tailoring substituent groups and the selection of cations or anions for charge balance can influence whether a particular MnIII- or MnIV-stabilizer compound will have wide band or narrow band corrosion inhibiting characteristics. Both inorganic or organic valence stabilizers may form compounds with the necessary physical properties of stability, solubility, and polarization to be effective corrosion inhibiting pigments.

TABLE 3


Wide and Narrow Band Valence Stabilizers for Trivalent
and/or Tetravalent Manganese Replacements for Hexavalent
Chromium or Tetravalent Lead Pigments

Hexavalent Chromium	Wide	Narrow
or Tetravalent Lead	Band Valence	Band Valence
Pigment to be Replaced	Stabilizers	Stabilizers

Zinc Chromates	Inorganic:	Inorganic:
(including basic forms)	Molybdates, tungstates,	Bismuthates,
Strontium Chromates	vanadates, niobates,	germanates,
Calcium Plumbate	tantalates, tellurates,	arsenates
	periodates, iodates,
	antimonates, stannates,
	sulfates, polyphosphates
	Organic:	Organic:
	See Table 4	See Table 5
Lead Chromates	Inorganic:	Inorganic:
(including basic forms)	Oxygen, titanates,	Carbonates
Lead Molybdate-Chromate	zirconates, tantalates,
Lead Silicochromate	aluminates, silicates,
	phosphates, borates
	Organic:	Organic:
	none	none
Red Lead	Inorganic:	Inorganic:
	Oxygen, titanates,	None
	zirconates, tantalates,
	aluminates, silicates
	Organic:	Organic:
	none	none

3a) Wide Band Inorganic Valence Stabilizers

Wide band inorganic valence stabilizers are formed around the MnIII or MnIV ion by “polymerizing” in synthesis solution. Inorganic wide band valence stabilizers for MnIII or MnIV for “sparingly soluble” pigments include molybdates (Mo ⁺⁶, Mo⁺⁵, or Mo⁺⁴, for example [Mn⁺⁴Mo₉O₃₂]⁶⁻ and [Mn⁺⁴Mo₁₂O₄₀]⁴⁻), tungstates (W⁺⁶, W⁺⁵, or W⁺⁴, for example [Mn⁺⁴W₁₂O₄₀]⁴− and [Mn⁺³ ₂W₂₂O₇₄]¹⁰⁻), vanadates (V⁺⁵and V⁺⁴, for example [Mn⁺⁴V₁₃O₃₈]⁷− and [Mn⁺⁴V₁₁O₃₂]⁵⁻), niobates (Nb⁺⁵and Nb⁺⁴, for example [Mn⁺⁴Nb₁₂O₃₈]¹²⁻), tantalates (Ta⁺⁵and Ta⁺⁴, for example [Mn⁺⁴Ta₁₂O₃₈]¹²⁻), tellurates (Te⁺⁶and Te⁺⁴, for example [Mn⁺⁴Te₃O₁₈]¹⁴−), periodates (1⁺⁷, for example [Mn⁺⁴I₃O₁₈]¹¹⁻), iodates (1⁺⁵, for example [Mn⁺⁴I₆O₁₈]²−), antimonates (Sb⁺⁵and Sb⁺³), stannates (Sn⁺⁴), sulfates (S⁺⁶, such as manganese spinels [Mn⁺³(SO₄)₂]¹⁻), and polyphosphates (P⁺⁵, for example [Mn⁺³P₃O₁₀]²⁻and [Mn⁺³P₂O₇]¹⁻). Many of these inorganics form octahedral and square pyramidal heteropolymetallate structures on precipitation from solution. For example, tellurate ions begin to polymerize near pH 5 in water and will complex with MnIII or MnIV ions in basic solution pH's. Therefore, as the pH is raised in the pigment synthesis bath, the tellurate ion polymerizes to polymorphs, which then complex the MnII or MnIV ion.

The general structural aspects of heteropolymetallates are well understood, and the stability of heteropolymetallates as a function of composition and structure is also well-characterized. The relatively unstable MnIII or MnIV ions are protected and stabilized within the surrounding octahedral and square pyramidal groups, although specific configurations of the heteropolymetallate anions differ from stabilizer to stabilizer (i.e., from molybdate to periodate or iodate). The dimensions of the octahedra and square pyramids are controlled by the size of the heteroatom (e.g., Mo, W, or Te) around which they are assembled.

A MnIII or MnIV ion trapped by the precipitation of these heteropolymetallates and its resulting “ion within a cage” structure can exhibit an even greater apparent volume due to the development of a large electrostatic double layer. This will influence both the valence stabilization of the MnIII or MnIV, as well as the solubility of the assembled compound. These compounds are reported to be excellent ion exchange agents for alkali ions. This caging structure serves to lower the solubility of the MnIII or MnIV because the chemical elements typically associated with these valence stabilizers (e.g., I, Te, Mo, or W) are all inherently less soluble in water than Mn. These materials can also establish oriented dipoles with the interior MnII or MnIV ion and form an electrostatic double layer during aqueous corrosion. Finally, the elements associated with these valence stabilizers themselves can contain high valence ions (i.e., V ⁺⁵, Te⁺⁶, or Mo⁺⁶), which will also serve somewhat in corrosion protection, although not to the degree of MnIII or MnIV (or CrVI), due to their lower redox potential.

Water-soluble precursors for these materials are generally used so that the synthesis can be carried out from aqueous solution. Many elements associated with these stabilizers (e.g., Mo, W, or Te) do not typically form water-soluble compounds so the identification of suitable precursors can be difficult.

Complex, partially-polymerized salts such as para- or meta-polymorphs for each compound may also be used as precursors. These polymorphs typically exhibit slightly lower solubilities in water than the simple salts. Peroxo-salts of these compounds, especially permolybdates, pertungstates, and pervanadates may also be used as precursors. Formation of the chosen heteropolymetallates from precursors such-as the fluorides, chlorides, bromides, nitrates, and perchlorates (e.g., SnCl ₄to form heterostannates and SbF₅to form heteroantimonates) can be difficult, but may be acceptable in certain circumstances. A valence stabilizer can be a cross between two or more of the wide-band inorganic valence stabilizers listed above. For example, a valence stabilizer composed of a periodate and a molybdate may be desirable in some situations. During the synthesis process, both of these materials will polymerize to form a mixed periodate/molybdate valence stabilizer out of the pigment solution.

The most notable valence stabilizer for low and insoluble MnIII and MnIV pigments is oxygen (O), as evidenced by the natural stability of such compounds as MnO ₂, Mn₃O₄, Mn₂O₃and MnOOH, all of which contain MnIII and/or MnIV ions. In instances where oxygen is used as a valence stabilizer for MnIII or MnIV, differences in addendum cations (i.e., Ca⁺²in CaMn₂O₄or Zn⁺²in ZnMn₂O₄) are observed to alter the solubility of the formed compound, and its performance as a corrosion inhibitor in a given binder system. This is discussed under Section 4 describing Additional Solubility Control Agents.

Additional wide band valence stabilizers for MnIII or MnIV for “low solubility” or “insoluble” pigments include silicates (Si ⁺⁴, for example [Mn⁺³Si₂O₆]¹⁻), borates (B⁺³, for example Mn⁺³ ₂B₄O₉), phosphates (P⁺⁵, for example Mn⁺³PO₄), titanates (Ti⁺⁴), zirconates (Zr⁺⁴), and aluminates (Al⁺³). These compounds can also form octahedral or square pyramids, but have a higher tendency to form chain-like structures during calcining or firing. Combinations of these materials, such as phosphosilicates, aluminosilicates, or borosilicates may also function as wide band valence stabilizers for low and insoluble MnIII and MnIV compounds.

3b) Wide Band Organic Valence Stabilizers

A variety of organic compounds meet the criteria to be typical wide band valence stabilizers for MnIII or MnIV. These coordination ligands produce MnIII or MnIV valence stabilized compounds that fulfill the general requirements of a MnIII or MnIV pigment material. Organic compounds can be very effective manganese stabilizers and provide the greatest degree of freedom in designing new manganese-stabilizer compounds with new functionalities. More possible organic valence stabilizer species exist than inorganic valence stabilizers because of the immense number of organic compounds and functionalities from which to choose. Water-soluble precursors for the organic valence stabilizers are generally used so that pigment synthesis can be carried out in aqueous solution. However, alcohol or hydrocarbon soluble species can also be used.

The number of wide band (and narrow band) organic compounds that are acceptable as valence stabilizers for trivalent or tetravalent manganese is limited. Common organic compounds such as alcohols, aldehydes, ketones, esters, ethers, alkyl or aromatic halides, most carboxylic acids, anhydrides, phenols, sulfonic acids, phosphonic acids, carbohydrates, waxes, fats, sugars, and oils are not as effective as the structural types described in these Tables to stabilize the trivalent or tetravalent manganese ion. At best, some of the organic types described in these Tables may presently be used for other industrial applications, but their incorporation into corrosion-inhibiting blends to stabilize trivalent or tetravalent manganese has heretofore been unrecognized.

The choice of substituent functional groups on these general classes of valence stabilizers will affect the physicochemical properties of the MnIII- or MnIV-containing compound and the corrosion resistance achieved using that compound. For example, the addition of —NH ₂or ═O substituents increases the net polarization of the overall net MnIII or MnIV/valence stabilizer compound, but will also increase its water solubility. Careful molecular design of MnIII and MnIV compounds is necessary in order to achieve desired performance characteristics.

In general, the bonding atoms in typical organic valence stabilizers are nitrogen, oxygen, or sulfur. Bonding atoms such as phosphorus, carbon, silicon, tin, arsenic, and antimony are much less desirable due to problems with valence stability, toxicity, or solubility. Other stable coordinations (like pentagonal bipyramidal) are known, even though these particular agents prefer octahedral or square pyramidal coordination with Mn ⁺³or Mn⁺⁴. These valence stabilizers all serve to stabilize the Mn⁺³or Mn⁺⁴ions within a sparingly soluble complex that can exhibit a polar character in aqueous solution.

TABLE 4


Wide Band Organic Valence Stabilizers
for the Mn⁺³and Mn⁺⁴Ions

General Structural Name
(Type of Organic)	Structural Representation

N Valence Stabilizer #1:	NH₃, NH₂R, NHR₂, and NR₃where R
Monoamines	represents H or any organic functional group
(N Monodentates)	wherein the number of carbon atoms ranges
	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/
	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N Valence Stabilizer #2:	R′—N—R—N—R″, where R, R′, and R″
Diamines	represent H or any organic functional group
(N—N Bidentates)	wherein the number of carbon atoms ranges
	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/
	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N Valence Stabilizer #3:	R—N—R′—N—R″—N—R′′′, where R, R′,
Triamines (either N—N	R″, and R′′′ represent H or any organic
Bidentates or N—N	functional group wherein the number of carbon
Tridentates)	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-insolubilizing/
	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N Valence Stabilizer #4:	R—N—R′—N—R″—N—R″′—N—R″″,
Tetramines (N—N	where R, R′, R″, R″′, and R″″ represent H or
Bidentates, N—N	any organic functional group wherein the
Tridentates, or N—N	number of carbon atoms ranges from 0 to 40,
Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N Valence Stabilizer #5:	R—N—R′—N—R″—N—R″′—N—R″″—
Pentamines (N—N	N—R″″′, where R, R′, R″, R″′, R″″, and
Bidentates, N—N	R″″′ represent H or any organic functional
Tridentates, or N—N	group wherein the number of carbon atoms
Tetradentates)	ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S,
	or P atoms.
N Valence Stabilizer #6:	R—N—R′—N—R″—N—R″′—N—R″″—
Hexamines (N—N	N—R″″′—N—R″″″, where R, R′, R″, R″′,
Bidentates, N—N	R″″, R″″′, and R″″″ represent H or any
Tridentates, N—N	organic functional group wherein the number
Tetradentates, or N—N	of carbon atoms ranges from 0 to 40,
Hexadentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N Valence Stabilizer #7:	Five membered heterocyclic ring containing
Five-Membered Heterocyclic	one, two, three, or four nitrogen atoms, all of
Rings containing One,	which may or may not function as binding
Two, Three, or Four	sites. Can include other ring systems bound
Nitrogen Atoms wherein at	to this heterocyclic ring, but they do not
least one Nitrogen Atom is	coordinate with the stabilized, high valence
a Binding Site (N	metal ion. Ring can also contain O, S, or P
Monodentates or N—N	atoms. This 5-membered ring and/or
Bidentates)	attached, uncoordinating rings may or may
	not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N Valence Stabilizer #8:	Six membered heterocyclic ring containing
Six-Membered Heterocyclic	one, two, three, or four nitrogen atoms, all
Rings containing One,	of which may or may not function as binding
Two, Three, or Four	sites. Can include other ring systems bound
Nitrogen Atoms wherein at	to this heterocyclic ring, but they do not
least one Nitrogen Atom is	coordinate with the stabilized, high valence
a Binding Site (N	metal ion. Ring can also contain O, S, or
Monodentates or N—N	P atoms. This 6-membered ring and/or
Bidentates)	attached, uncoordinating rings may or may
	not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N Valence Stabilizer #9:	Five membered heterocyclic ring(s)
Five-Membered Heterocyclic	containing one, two, three, or four nitrogen
Rings containing One,	atoms. In addition, ligand contains additional
Two, Three, or Four	nitrogen-containing substituents (usually
Nitrogen Atoms and having	amines) that constitute N binding sites. Can
at least one additional	include other ring systems bound to the
Nitrogen Atom Binding	heterocyclic ring or to the N-containing
Site not in a Ring (N	substituent, but they do not coordinate with
Monodentates, N—N	the stabilized, high valence metal ion.
Bidentates, N	Ring(s) can also contain O, S, or P atoms.
Tridentates, N—N	This 5-membered ring(s) and/or attached,
Tetradentates, or	uncoordinating rings and/or N containing
N—N Hexadentates)	substituent(s) may or may not have halogen
	or polarizing or water-insolubilizing/
	solubilizing groups attached.
N Valence Stabilizer #10:	Six membered heterocyclic ring(s)
Six-Membered Heterocyclic	containing one, two, three, or four nitrogen
Rings containing One,	atoms. In addition, ligand contains additional
Two, Three, or Four	nitrogen-containing substituents (usually
Nitrogen Atoms at least one	amines) that constitute N binding sites. Can
additional Nitrogen Atom	include other ring systems bound to the
Binding Site not in a Ring	heterocyclic ring or to the N-containing
(N Monodentates, N—N	substituent, but they do not coordinate with
Tridentates, N—N	the stabilized, high valence metal ion.
Tetradentates, or N—N	Ring(s) can also contain O, S, or P atoms.
Bidentates, N—N	This 6-membered ring(s) and/or attached,
Hexadentates)	uncoordinating rings and/or N-containing
	substituent(s) may or may not have halogen
	or polarizing or water-insolubilizing/
	solubilizing groups attached.
N Valence Stabilizer #11:.	Five membered heterocyclic ring(s)
Five-Membered Heterocyclic	containing one, two, three, or four nitrogen
Rings containing One,	atoms. In addition, ligand contains additional
Two, Three, or Four	nitrogen-containing rings that constitute N
Nitrogen Atoms at least	binding sites. Can include other ring systems
one additional Nitrogen	bound to the N-containing heterocyclic rings,
Atom Binding Site in a	but they do not coordinate with the
Separate Ring (N	stabilized, high valence metal ion. Ring(s)
Monodentates, N—N	can also contain O, S, or P atoms. This
Bidentates, N—N	5-membered ring(s) and/or additional N-
Tridentates, N—N	containing ring(s) and/or attached,
Tetradentates)	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N Valence Stabilizer #12:	Six membered heterocyclic ring(s)
Six-Membered Heterocyclic	containing one, two, three, or four nitrogen
Rings containing One,	atoms. In addition, ligand contains additional
Two, Three, or Four	nitrogen-containing rings that constitute N
Nitrogen Atoms at least one	binding sites. Can include other ring systems
additional Nitrogen Atom	bound to the N-containing heterocyclic
Binding Site in a Separate	rings, but they do not coordinate with the
Ring (N Monodentates,	stabilized, high valence metal ion. Ring(s)
N—N Bidentates, N—N	can also contain O, S, or P atoms. This
Tridentates, N—N	6-membered ring(s) and/or additional N-
Tetradentates)	containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N Valence Stabilizer #13:	Macrocyclic ligands containing two, three,
Two-, Three-, Four-, Six-,	four, six, eight, or ten nitrogen binding sites
Eight-, and Ten- Membered	to valence stabilize the central metal ion.
Macrocyclics,	Can include other hydrocarbon or ring
Macrobicyclics, and	systems bound to this macrocyclic ligand,
Macropolycyclies	but they do not coordinate with the
(including Catapinands,	stabilized, high valence metal ion. This
Cryptands, Cyclidenes, and	ligand and/or attached, uncoordinating hydrocarbons/rings may or may
Sepulchrates) wherein all	not have halogen or polarizing or water-
Binding Sites are composed	insolubilizing/solubilizing groups attached.
of Nitrogen (usually amine
or imine groups) and are
not contained in
Component Heterocyclic
Rings (N—N Bidentates,
N—N Tridentates, N—N
Tetradentates, and N—N
Hexadentates)
N Valence Stabilizer #14:	Macrocyclic ligands containing a total of
Four-, Six-, Eight-, or	four, six, eight, or ten five-membered
Ten-Membered Macro-	heterocyclic rings containing nitrogen
cyclics, Macrobicyclics,	binding sites. Can include other
and Macropolycyclics	hydrocarbon/ring systems bound to this
(including Catapinands,	macrocyclic ligand, but they do not
Cryptands, Cyclidenes, and	coordinate with the stabilized, high valence
Sepulchrates) wherein all	metal ion. This ligand and/or attached,
Binding Sites are composed	uncoordinating hydrocarbon/rings may or
of Nitrogen and are	may not have halogen or polarizing or
contained in Component	water-insolubilizing groups attached.
5-Membered Heterocyclic
Rings (N—N Bidentates,
N—N Tridentates, N—N
Tetradentates, or N—N
Hexadentates)
N Valence Stabilizer #15:	Macrocyclic ligands containing at least one
Four-, Six-, Eight-, or Ten-	5-membered heterocyclic ring. These
Membered Macrocyclics,	heterocyclic rings provide nitrogen binding
Macrobicyclics, and	sites to valence stabilize the central metal
Macropolycyclics	ion. Other amine or imine binding sites can
(including Catapinands,	also be included in the macrocyclic ligand,
Cryptands, Cyclidenes,	so long as the total number of binding sites
and Sepulchrates)	is four, six, eight, or ten. Can include other
wherein all Binding Sites	hydrocarbon/ring systems bound to this
are composed of Nitrogen	macrocyclic ligand, but they do not
and are contained in a	coordinate with the stabilized, high valence
Combination of 5-	metal ion. This ligand and/or attached,
Membered Heterocyclic	uncoordinating hydrocarbon/rings may or may
Rings and Amine or Imine	not have halogen or polarizing or water-
Groups (N—N Bidentates,	insolubilizing groups attached.
N—N Tridentates, N—N
Tetradentates, or N—N
Hexadentates)
N Valence Stabilizer #16:	Macrocyclic ligands containing a total of
Four-, Six-, Eight-, or Ten-	four, six, eight, or ten six-membered
Membered Macrocyclics,	heterocyclic rings containing nitrogen
Macrobicyclics, and	binding sites. Can include other
Macropolycyclics	hydrocarbon/ring systems bound to this
(including Catapinands,	macrocyclic ligand, but they do not
Cryptands, Cyclidenes, and	coordinate with the stabilized, high valence
Sepulchrates) wherein all	metal ion. This ligand and/or attached,
Binding Sites are composed	uncoordinating hydrocarbon/rings may or
of Nitrogen and are	may not have halogen or polarizing or water-
contained in Component	insolubilizing groups attached.
6-Membered Heterocyclic
Rings (N—N Bidentates,
N—N Tridentates, N—N
Tetradentates, or N—N
Hexadentates)
N Valence Stabilizer #17:	Macrocyclic ligands containing at least one
Four-, Six-, Eight-, or Ten-	6-membered heterocyclic ring. These
Membered Macrocyclics,	heterocyclic rings provide nitrogen binding
Macrobicyclics, and	sites to valence stabilize the central metal
Macropolycyclics	ion. Other amine or imine binding sites can
(including Catapinands,	also be included in the macrocyclic ligand,
Cryptands, Cyclidenes,	so long as the total number of binding
and Sepulchrates)	sites is four, six, eight, or ten. Can include
wherein all Binding Sites	other hydrocarbon/ring systems bound to
are composed of Nitrogen	this macrocyclic ligand, but they do not
and are contained in a	coordinate with the stabilized, high valence
Combination of 6-	metal ion. This ligand and/or attached,
Membered Heterocyclic	uncoordinating hydrocarbon/rings may or
Rings and Amine or Imine	may not have halogen or polarizing or water-
Groups (N—N Bidentates,	insolubilizing groups attached.
N—N Tridentates, N—N
Tetradentates, or N—N
Hexadentates)

N Valence Stabilizer #18:	R′—NH—C(—R)═N—R″, where R, R′,
Amidines and Diamidines	and R″represent H or any organic functional
(N—N Bidentates and	group wherein the number of carbon atoms
N—N Tetradentates)	ranges from 0 to 40, optionally having
	halogen or polarizing or water-insolubilizing/
	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N Valence Stabilizer #19:	RR′—N—C(═NH)—NR″—C(═NH)—
Biguanides	NR″′R″″ for biguanides, RR′—N—
(Imidodicarbonimidic	C(═NH)—NR″—NH—C(═NH)—NR″′R″″
Diamides or Dihydrazides),	for biguanidines, where R, R′, R″, R″′, and
Biguanidines,	R″″ represent H, NH₂, or any organic
Imidotricarbonimidic	functional group wherein the number of
Diamides or Dihydrazides,	carbon atoms ranges from 0 to 40, halogen
Imidotetracarbonimidic	or polarizing or water-insolubilizing/
Diamides or Dihydrazides,	solubilizing groups attached. Ligand can also
Dibiguanides,	contain nonbinding N, O, S, or P atoms.
Bis(biguanidines),
Polybiguanides, and
Poly(biguanidines) (N—N
Bidentates, N—N
Tridentates, N—N
Tetradentates, and N—N
Hexadentates)
N Valence Stabilizer #20:	RR′—N—C(═NH)—CR″R′″—C(═NH)—
Diamidinomethanes,	NR″″R″″′, where R, R′, R″, R″′, R″″, and
Bis(amidinomethanes), and	R″″′ represent H, NH₂, or any organic
Poly(amidinomethanes)	functional group wherein the number of
(N—N Bidentates, N—N	carbon atoms ranges from 0 to 40, optionally
Tridentates, N—N	having halogen or polarizing or water-
Tetradentates, and	insolubilizing/solubilizing groups attached.
N—N Hexadentates)	Ligand can also contain nonbinding N, O, S,
	or P atoms.
N Valence Stabilizer #21:	RR′—N—C(═NH)—NR″—C(═NH)—R″′
Imidoylguanidines,	for imidoylguanidines, and RR′—N—
Amidinoguanidines,	C(═NH)—NR″—NH—C(NH)—R″′ for
Bis(imidoylguanidines),	amidinoguanidines, where R, R′, R″, and
Bis(amidinoguanidines),	R″′ represent H, NH₂, or any organic
Poly(imidoylguanidines),	functional group wherein the number of
and Poly(amidino-	carbon atoms ranges from 0 to 40, optionally
guanidines) (N—N	having halogen or polarizing or water-
Bidentates, N—N	insolubilizing/solubilizing groups attached.
Tridentates, N—N	Ligand can also contain nonbinding N, O, S,
Tetradentates)	or P atoms.
N Valence Stabilizer #22:	RR′—N—C(NH)—O—C(═NH)-NR″R″′,
Diformamidine oxides	where R, R′, R″, and R″′ represent H, NH₂,
(Dicarbonimidic Diamides	or any organic functional group wherein the
or Dihydrazides),	number of carbon atoms ranges from 0 to 40,
Tricarbonimidic Diamides	optionally having halogen or polarizing or
or Dihydrazides,	water-insolubilizing/solubilizing groups
Tetracarbonimidic	attached. Ligand can also contain nonbinding
Diamides or Dihydrazides,	N, O, S, or P atoms.
Bis(diformamidine oxides),
and Poly(diformamidine
oxides) (N—N Bidentates,
N—N Tridentates,
N—N Tetradentates)
N Valence Stabilizer #23:	RR′—N—C(═NH)—S—C(═NH)—
Diformamidine Sulfides	NR″R″′, where R, R′, R″, and R″′ represent
(Thiodicarbonimidic	H, NH₂, or any organic functional group
Diamides or Dihydrazides),	wherein the number of carbon atoms ranges
Thiotricarbonimidic	from 0 to 40, optionally having halogen or
Diamides or Dihydrazides,	polarizing or water-insolubilizing/
Thiotetracarbonimidic	solubilizing groups attached. Ligand can also
Diamides or Dihydrazides,	contain nonbinding N, O, S, or P atoms.
Bis(diformamidine
sulfides), and
Poly(diformamidine
sulfides) (N—N
Bidentates, N—N
Tridentates, N—N
Tetradentates)
N Valence Stabilizer #24:	R—O—C(═NH)—NR′—C(═NH)—O—R′
Imidodicarbonimidie Acids,	for imidodicarbomimidic acids, and R—O—
Diimidodicarbonimidic	C(═NH)—NR′—NH—C(═NH)—O—R″
Acids, Imidotricarbon-	for diimidodicarbonimidic acids, where R,
imidic Acids, Imidotetra-	R′, and R″ represent H, NH₂, or any organic
carbonimidic Acids, and	functional group wherein the number of
derivatives thereof (N—N	carbon atoms ranges from 0 to 40, optionally
Bidentates, N—N	having halogen or polarizing or water-
Tridentates, N—N	insolubilizing/solubilizing groups attached.
Tetradentates, and	Ligand can also contain nonbinding N, O, S,
N—N Hexadentates)	or P atoms.
N Valence Stabilizer #25:	R—S—C(═NH)—NR′—C(═NH)—S—R″
Thioimidodicarbonimidic	for thioimidodicarbonimidic acids, and R—
Acids, Thiodiimidodi-	S—C(═NH)—NR′—NH—C(═NH)—S
carbonimidic Acids,	—R″ for thiodiimidodicarbonimidic acids,
Thioimidotricarbonimidic	where R, R′, and R″ represent H, NH₂, or
Acids, Thioimidotetra-	any organic functional group wherein the
carbonimidic Acids, and	number of carbon atoms ranges from 0 to 40,
derivatives thereof	optionally having halogen or polarizing or
(N—N Bidentates, N—N	water-insolubilizing/solubilizing groups
Tridentates, N—N	attached. Ligand can also contain nonbinding
Tetradentates, and	N, O, S, or P atoms.
N—N Hexadentates)
N Valence Stabilizer #26:	R—C(═NH)—NR′—C(═NH)—R″ for
Diimidoylimines,	diimidoylimines, and R—C(═NH)—NR′—
Diimidoylhydrazides,	NH—C(═NH)—R″ for diimidoyl-
Bis(diimidoylimines),	hydrazides, where R, R′, and R″ represent
Bis(diimidoylhydrazides),	H, NH₂, or any organic functional group
Poly(diimidoylimines), and	wherein the number of carbon atoms ranges
Poly(diimidoylhydrazides)	from 0 to 40, optionally having halogen or
(N—N Tridentates and	polarizing or water-insolubilizing/
N—N Hexadentates)	solubilizing groups attached. Ligand can
	also contain nonbinding N, O, S, or
	P atoms.
N Valence Stabilizer #27:	RR′—N—S(═NH)(═O)—OR″ or RR′—
Imidosulfamides,	N—S(═NH)(═O)—N—R″R″′ for
Diimidosulfamides,	imidosulfamides, and RR′—N—
Bis(imidosulfamides),	S(═NH)(═NH)—OR″ or RR′—N—
Bis(diimidosulfamides),	S(═NH)(═NH)—N—R″R″′ for diimido-
Poly(imidosulfamides), and	sulfamides, where R, R′, R″, and R″′
Poly(diimidosulfamides)	represent H, NH₂, or any organic functional
(N—N Bidentates, N—N	group wherein the number of carbon atoms
Tridentates, N—N	ranges from 0 to 40, optionally having
Tetradentates, and	halogen or polarizing or water-insolubilizing/
N—N Hexadentates)	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N Valence Stabilizer #28:	(NH═)P(—NRR′)(—NR″R″′)(—NR″″R″″′),
Phosphoramidimidic	where R, R′, R″, R″′, R″″, and R″″′ represent
Triamides, Bis(phosphor-	H, NH₂, or any organic functional group
amidimidic triamides), and	wherein the number of carbon atoms ranges
Poly(phosphoramidimidic	from 0 to 40, optionally having halogen or
triamides) and derivatives	polarizing or water-insolubilizing/
thereof (N—N Bidentates,	solubilizing groups attached. Ligand can also
N—N Tridentates, N—N	contain nonbinding N, O, S, or P atoms.
Tetradentates, and N—N
Hexadentates)
N Valence Stabilizer #29:	(NH═)P(—NRR′)(OH)₂for phosphor-
Phosphoramidimidic Acid,	amidimidic acid, and (NH═)P(—NRR′)
Phosphorodiamidimidic	(—NR″R″′)(OH) for phosphorodiamidimidic
Acid, Bis(Phosphor-	acid, where R, R′, R″, and R″′ represent H,
amidimidic Acid),	NH₂, or any organic functional group
Bis(Phosphorodiamidimidic	wherein the number of carbon atoms ranges
Acid), Poly(Phosphor-	from 0 to 40, optionally having halogen or
amidimidic Acid), and	polarizing or water-insolubilizing/
Poly(Phosphorodi-	solubilizing groups attached. Ligand can also
amidimidic Acid),	contain nonbinding N, O, S, or P atoms.
derivatives thereof
(N—N Bidentates, N—N
Tridentates, N—N
Tetradentates, and N—N
Hexadentates)
N Valence Stabilizer #30:	(NH═)P(—NRR′)(SH)₂for phos-
Phosphoramidimidodithioic	phoramidimidodithioic acid, and (NH═)P(—
Acid, Phosphorodiamidi-	NRR′)(—NR″R″′)(SH) for
midothioic Acid, Bis(Phos-	phosphorodiamidimidothioic acid, where R,
phoramidimidodithioic	R′, R″, and R″′ represent H, NH₂, or any
Acid), Bis(Phosphorodi-	organic functional group wherein the number
amidimidothioic Acid),	of carbon atoms ranges from 0 to 40,
Poly(Phosphoramidimido-	optionally having halogen or polarizing or
dithioic Acid), Poly(Phos-	water-insolubilizing/solubilizing groups
phorodiamidimidothioic	attached. Ligand can also contain nonbinding
Acid), and derivatives	N, O, S, or P atoms.
thereof (N—N Bidentates,
N—N Tridentates,
N—N Tetradentates,
and N—N Hexadentates)
N Valence Stabilizer #31:	R—N═N—R′ for azo compounds,
Azo compounds including	R—N═—NH—R′ for triazenes, where
triazenes with amino,	R, and R′ represent H or any organic
imino, oximo, diazeno, or	functional group wherein the number of
hydrazido substitution at	carbon atoms ranges from 0 to 40, optionally
the ortho- (for aryl) or	having halogen or polarizing or water-
alpha- or beta- (for alkyl)	insolubilizing/solubilizing groups attached.
positions, Bis[o-(H₂N—)	(Must include ortho-amino, imino, oximo,
or alpha- or beta-	diazeno, or hydrazido substituted aryl azo
(H₂N—)azo compounds],	compounds, and alpha- or beta-amino,
or Poly[o-(H₂N—) or	imino, oximo, diazeno, or hydrazido alkyl
alpha- or beta-(H2N—)azo	azo compounds.) Ligand can also contain
compounds) (N—N	nonbinding N, O, S, or P atoms.
Bidentates, N—N
Tridentates, N—N
Tetradentates, or
N—N Hexadentates)
N Valence Stabilizer #32:	R—N═N—C(═NH)—NR′R″ for diazene-
Diazeneformimidamides	formimidamides, and R—N═N—CR′R″—
(Diazeneamidines),	C(═NH)—NR″′R″″ for diazeneacetimid-
Diazeneacetimidamides	amides, where R, R′, R″, R″′, and R″″
(Diazene-alpha-amidino-	represent H, NH₂, or any organic functional
alkanes(alkenes)), Bis(di-	group wherein the number of carbon atoms
azeneformimidamides),	ranges from 0 to 40, optionally having
Bis(diazeneacetimid-	halogen or polarizing or water-insolubilizing/
amides), Poly(diazene-	solubilizing groups attached. Ligand can also
formimidamides), and	contain nonbinding N, O, S, or P atoms.
Poly(diazeneacetimid-
amides) (N—N Bidentates,
N—N Tetradentates,
and N—N Hexadentates)
N Valence Stabilizer #33:	R—N═N—C(═NH)—OR′ for diazene-
Diazeneformimidic Acid,	formimidic acid, and R—N═N—CR′R″—
Diazeneacetimidic Acid,	C(═NH)—OR″′ for diazeneacetimidic acid,
Bis(diazeneformimidic	where R, R′, R″, and R″′ represent H, NH₂,
acid), Bis(diazene-	or any organic functional group wherein the
acetimidic acid),	number of carbon atoms ranges from 0 to 40,
Poly(diazeneformimidic	optionally having halogen or polarizing or
acid), Poly(diazene-	water-insolubilizing/solubilizing groups
acetimidic acid), and	attached. Ligand can also contain nonbinding
Bidentates, N—N	N, O, 5, or P atoms.
Tetradentates, and
N—N Hexadentates)
N Valence Stabilizer #34:	R—N═N—C(═NH)—SR′ for diazene-
Diazeneformimidothioic	formimidothioic acid, and R—NN—
Acid, Diazeneacetimido-	CR′R″—C(═NH)—SR″′ for diazene-
thioic Acid, Bis(diazene-	acetimidothioic acid, where R, R′, R″, and
formimidothioic acid),	R″′ represent H, NH₂, or any organic
Bis(diazeneacetimidothioic	functional group wherein the number of
acid), Poly(diazene-	carbon atoms ranges from 0 to 40, optionally
formimidothioic acid),	having halogen or polarizing or water-
Poly(diazeneacetimido-	insolubilizing/solubilizing groups attached.
thioic acid), and	Ligand can also contain nonbinding N, O, S,
derivatives thereof	or P atoms.
(N—N Bidentates,
N—N Tetradentates,
and N—N Hexadentates)
N Valence Stabilizer #35:	R—N═N—C(NH)—R′ or R—N═N—
Imidoyldiazenes,	CR′R″—C(═NH)—R″′, where R, R′, R″,
Bis(imidoyldiazenes), and	and R″′represent H, NH₂, or any organic
Poly(imidoyldiazenes),	functional group wherein the number of
(N—N Bidentates,	carbon atoms ranges from 0 to 40, optionally
N—N Tetradentates	having halogen or polarizing or water-
and N—N Hexadentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S,
	or P atoms.
N Valence Stabilizer #36:	RR′—N—C(═NH)—N═N—C(═NH)—
Diazenediformimidamides	NR″R″′ for diazenediformimidamides, and
(1,2-Diazenediamidines),	RR′—N—C(═NH)—CR″R″′—N═N—
Diazenediacetimidamides	CR″″R″″′—C(═NH)—NR″″″R″″″′
(1,2-Diazene-di-alpha-	for diazenediacetimidamides, where R, R′,
amidinoalkanes(alkenes)),	R″, R′″, R″″, R″″′, R″″″, and R″″″′ represent
Bis(diazenediformimid-	H, NH₂, or any organic functional group
amides), Bis(diazenedi-	wherein the number of carbon atoms ranges
acetimidamides), Poly(di-	from 0 to 40, optionally having halogen or
azenediformimidamides),	polarizing or water-insolubilizing/
and Poly(diazenedi-	solubilizing groups attached. Ligand can also
acetimidamides) (N—N	contain nonbinding N, O, S, or P atoms.
Tridentates and N—N
Hexadentates)
N Valence Stabilizer #37:	RO—C(═NH)—N═N—C(═NH)—OR′
Diazenediformimidic Acid,	for diazenediformimidic acid, and RO—
Diazenediacetimidic Acid,	C(═NH)—CR′R″—N═N—CR″′R″″—
Bis(diazenediformimidic	C(═NH)—OR″″′ for diazenediacetimidic
acid), Bis(diazenedi-	acid, where R, R′, R″, R″′, R″″, and R″″′
acetimidic acid),	represent H, NH₂, or any organic functional
Poly(diazenediformimidic	group wherein the number of carbon atoms
acid), and Poly(diazenedi-	ranges from 0 to 40, optionally having
acetimidic acid), and	halogen or polarizing or water-insolubilizing/
derivatives thereof	solubilizing groups attached. Ligand can also
(N—N Tridentates	contain nonbinding N, O, S, or P atoms.
and N—N Hexadentates)
N Valence Stabilizer #38:	RS—C(═NH)—N═N—C(═NH)—SR′ for
Diazenediformimidothioic	diazenediformimidothioic acid, and RS—
Acid, Diazenediacetimido-	C(═NH)—CR′R″—N═N—CR″′R″″—
thioic Acid, Bis(diazene-	C(═NH)—SR″″′ for diazenediacetimi-
diformimidothioic acid),	dothioic acid, where R, R′, R″, R″′, R″″, and
Bis(diazenediacetimido-	R″″′ represent H, NH₂, or any organic
thioic acid), Poly(diazene-	functional group wherein the number of
diformimidothioic acid),	carbon atoms ranges from 0 to 40, optionally
and Poly(diazenedi-	having halogen or polarizing or water-
acetimidothioic acid), and	insolubilizing/solubilizing groups attached.
derivatives thereof	Ligand can also contain nonbinding N, O, S,
(N—N Tridentates and	or P atoms.
N—N Hexadentates)
N Valence Stabilizer #39:	R—C(═NH)—N═N—C(NH)—R″or
Diimidoyldiazenes,	R—C(═NH)—CR′R″—N═N—CR″′R″″—
Bis(diimidoyldiazenes),	C(═NH)—R″″′, where R, R′, R″, R″′, R″″,
and Poly(diimidoyl-	and R″″′ represent H, NH₂, or any organic
diazenes), (N—N	functional group wherein the number of
Tridentates and N—N	carbon atoms ranges from 0 to 40, optionally
Hexadentates)	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N,
	O, S, or P atoms.
N Valence Stabilizer #40:	R—N═N—CR′═N—NR″R″′, where R, R′,
Ortho-amino (or	R″, and R″′ represent H, or any organic
-hydrazido) Substituted	functional group wherein the number of
Formazans, Bis(o-amino or	carbon atoms ranges from 0 to 40, optionally
-hydrazido substituted	having halogen or polarizing or water-
formazans), and Poly(o-	insolubilizing/solubilizing groups attached.
amino or -hydrazido	(Must include ortho-amine or hydrazide
substituted formazans)	substituted aryl R derivatives, and beta-
(N—N Bidentates, N—N	amine or hydrazide substituted alkyl R
Tridentates, N—N	derivatives.) Ligand can also contain
Tetradentates, and N—N	nonbinding N, O, S, or P atoms.
Hexadentates)
N Valence Stabilizer #41:	RR′C═N—N═CR″R″′ or RR′C═N—
Ortho-amino (or	NR″R″′ (for ketazines), where R, R′, R″,
-hydrazido) Substituted	and R″′ represent H, or any organic
Azines (including	functional group wherein the number of
ketazines), Bis(o-amino	carbon atoms ranges from 0 to 40, optionally
or hydrazido substituted	having halogen or polarizing or water-
azines), and Poly(o-amino	insolubilizing/solubilizing groups
or hydrazido substituted	attached. (Must include ortho-amine or
azines) (N —N Bidentates,	hydrazide substituted aryl R derivatives, and
N—N Tridentates,	beta-amine or hydrazide substituted alkyl R
N—N Tetradentates, and	derivatives.) Ligand can also contain
N—N Hexadentates)	nonbinding N, O, S, or P atoms.
N Valence Stabilizer #42:	RR′C═N—R″, where R, R′, and R″
Schiff Bases with one	represent H, or any organic functional group
Imine (C═N) Group and	wherein the number of carbon atoms ranges
with ortho- or alpha- or	from 0 to 40, optionally having halogen or
beta-amino or imino or	polarizing or water-insolubilizing/
oximo or diazeno or	solubilizing groups attached. (Must contain
hydrazido substitution	ortho- or alpha- or beta-amino or imino or
(N—N Bidentates, N—N	oximo or diazeno or hydrazido substitution.)
Tridentates, N—N	Ligand can also contain nonbinding N, O, S,
Tetradentates, N—N	or P atoms.
Pentadentates, or N—N
Hexadentates). Also
includes hydrazones with
ortho-N substitution.
N Valence Stabilizer #43:	RR′C═N—R″—N═CR″′R″″ or
Schiff Bases with two	R—N═C—R′—CN—R′ or
Imine (C═N) Groups	RC═N—R′—N═CR″, where R, R′, R″,
and without ortho- (for aryl	R″′, and R″″ represent H, or any organic
constituents) or alpha-	functional group wherein the number of
or beta- (for alkyl	carbon atoms ranges from 0 to 40, optionally
constituents) hydroxy,	having halogen or polarizing or water-
carboxy, carbonyl, thiol,	insolubilizing/solubilizing groups attached.
mercapto, thiocarbonyl,	(Not including ortho-, alpha-, or beta-
amino, imino, oximo,	hydroxy, carboxy, carbonyl, thiol, mercapto,
diazeno, or hydrazido	thiocarbonyl, amino, imino, oximo, diazeno,
substitution (N—N	or hydrazido substitution.) Ligand can also
Bidentates). Also includes	contain nonbinding N, O, S, or P atoms.
dihydrazones.
N Valence Stabilizer #44:	RR′C═N—R″—N═CR″′R″″ or
Schiff Bases with two	R—N═C—R′—C═N—R′ or
Imine (C═N) Groups and	RC═N—R′—N═CR″, where R, R′, R″,
with ortho- or alpha- or	R″′, and R″″ represent H, or any organic
beta-amino or imino or	functional group wherein the number of
oximo or diazeno or	carbon atoms ranges from 0 to 40, optionally
hydrazido substitution	having halogen or polarizing or water-
(N—N Tridentates,	insolubilizing/solubilizing groups attached.
N—N Tetradentates,	(Must contain ortho- or alpha- or beta-amino
N—N Pentadentates, or	or imino or oximo or diazeno or hydrazido
N—N Hexadentates).	substitution.) Ligand can also contain
Also includes hydrazones	nonbinding N, O, S, or P atoms.
with ortho-N substitution.
N Valence Stabilizer #45:	N(—R—N═CR′R″)₃, where R, R′, and R″
Schiff Bases with three	represent H, or any organic functional group
Imine (C═N) Groups and	wherein the number of carbon atoms ranges
without ortho- (for aryl	from 0 to 40, optionally having halogen or
constituents) or alpha-	polarizing or water-insolubilizing/
or beta- (for alkyl	solubilizing groups attached. (Not including
constituents) hydroxy,	ortho-, alpha-, or beta-hydroxy, carboxy,
carboxy, carbonyl, thiol,	carbonyl, thiol, mercapto, thiocarbonyl,
mercapto, thiocarbonyl,	amino, imino, oximo, diazeno, or hydrazido
amino, imino, oximo,	substitution.) Ligand can also contain
diazeno, or hydrazido	nonbinding N, O, S, or P atoms.
substitution (N—N
Tridentates). Also includes
trihydrazones.
N Valence Stabilizer #46:	N(—R—N═CR′R″)₃, where R, R′, and R″
Schiff Bases with three	represent H, or any organic functional group
Imine (C═N) Groups and	wherein the number of carbon atoms ranges
with ortho- or alpha- or	from 0 to 40, optionally having halogen or
beta-amino or imino or	polarizing or water-insolubilizing/
oximo or diazeno or	solubilizing groups attached. (Must contain
hydrazido substitution	ortho- or alpha- or beta-amino or imino or
(N—N Tetradentates,	oximo or diazeno or hydrazido substitution.)
N—N Pentadentates,	Ligand can also contain nonbinding N, O, S,
or N—N Hexadentates)	or P atoms.
S Valence Stabilizer #1:	Macrocyclic ligands containing two, four,
Macrocyclic,	or six thioketone binding sites to valence
Macrobicyclic, and	stabilize the central metal ion. Can include
Macropolycyclic	other hydrocarbon or ring systems bound to
Oligothioketones	this macrocyclic ligand, but they do not
(including Catapinands,	coordinate with the stabilized, high valence
Cryptands, Cyclidenes, and	metal ion. This ligand and/or attached,
Sepulchrates) wherein all	uncoordinating hydrocarbons/rings may or
Binding Sites are composed	may not have halogen or polarizing or
of Thioketones (typically	water-insolubilizing/solubilizing groups
in the beta position) (S—S	attached.
Bidentates, S—S
Tetradentates, and S—S
Hexadentates)
S Valence Stabilizer #2:	Macrocyclic ligands containing two, four,
Macrocyclic,	six, or eight 1,1-dithiolene binding sites to
Macrobicyclic, and	valence stabilize the central metal ion. Can
Macropolycyclic	include other hydrocarbon or ring systems
Dithiolenes (including	bound to this macrocyclic ligand, but they do
Catapinands, Cryptands,	not coordinate with the stabilized, high
Cyclidenes, and	valence metal ion. This ligand and/or
Sepulchrates) wherein all	attached, uncoordinating hydrocarbons/rings
Binding Sites are	may or may not have halogen or polarizing
composed of alpha, alpha	or water-insolubilizing/solubilizing groups
dithiols (meaning two thiol	attached.
groups on a single carbon
atom in the ring) (S—S
Bidentates, S—S
Tetradentates, and
S—S Hexadentates)
S Valence Stabilizer #3:	RC(═S)—NR′—C(═S)—R″ for dithio-
Dithiolmidodialdehydes,	imidodialdehydes, and RC(═S)—NR′—
Dithiohydrazidodialdehydes	NH—C(═S)—R″ for dithiohydrazidodi-
(thioacyl thiohydrazides),	aldehydes (thioacyl thiohydrazides), where R,
Bis(dithioimidodi-	R′, and R″ represent H, NH₂, or any
aldehydes), Bis(dithio-	organic functional group wherein the number
hydrazidodialdehydes),	of carbon atoms ranges from 0 to 40,
Poly(dithioimidodi-	optionally having halogen or polarizing or
aldehydes), and Poly(di-	water-insolubilizing/solubilizing groups
thiohydrazidodialdehydes)	attached. Ligand can also contain nonbinding
(S—S Bidentates,	N, O, S, or P atoms.
S—S Tridentates,
S—S Tetradentates)
S Valence Stabilizer #4:	R—O—C(═S)—NR′—C(═S)—O—R″ or
Dithioimidodicarbonic	R—S—C(═S)—NR′—C(═S)—S—R″ for
acids, Dithiohydrazidodi-	dithioimidodicarbonic acids, and R—O—
carbonic acids, Bis(dithio-	C(═S)—NR′—NH—C(═S)—O—R″ or
imidodicarbonic acids),	R—S—C(═S)—NR′—NH—C(═S)—S—
Bis(dithiohydrazidodi-	R″ for dithiohydrazidodicarbonic acids,
carbonic acids), Poly(di-	where R, R′, and R″represent H, NH₂, or
thioimidodicarbonic acids),	any organic functional group wherein the
Poly(dithiohydrazidodi-	number of carbon atoms ranges from 0 to 40,
carbonic acids) and	optionally having halogen or polarizing or
derivatives thereof	water-insolubilizing/solubilizing groups
(S—S Bidentates,	attached. Ligand can also contain
S—S Tridentates,	nonbinding N, O, S, or P atoms.
S—S Tetradentates)
S Valence Stabilizer #5:	R—C(═S)—CR′R″—C(═S)—R″′ where
1,3-Dithioketones (Dithio-	R, R′, R″, and R″′ represent H, NH₂, or
beta-ketonates), 1,3,5-	any organic functional group wherein the
Trithioketones, Bis(1,3-	number of carbon atoms ranges from 0 to 40,
Dithioketones), and	optionally having halogen or polarizing or
Poly(1,3-Dithioketones)	water-insolubilizing/solubilizing groups
(S—S Bidentates, S—S	attached. Ligand can also contain
Tridentates, S—S	nonbinding N, O, S, or P atoms.
Tetradentates)
S Valence Stabilizer #6:	R—C(═S)—C(═S)—R′ where R and R′
1,2-Dithioketones	represent H, NH₂, or any organic functional
(Dithiolenes, Dithio-	group wherein the number of carbon atoms
alpha-ketonates), 1,2,3-	ranges from 0 to 40, optionally having
Trithioketones,	halogen or polarizing or water-insolubilizing/
Dithiotropolonates,	solubilizing groups attached. Ligand can also
ortho-Dithioquinones,	contain nonbinding N, O, S, or P atoms.
Bis(1,2-Dithioketones), and
Poly(1,2-Dithioketones)
(S—S Bidentates,
S—S Tridentates,
S—S Tetradentates)
S Valence Stabilizer #7:	RR′—N—C(═S)—CR″R″′—C(═S)—N—
Dithiomalonamides	R″″R′″″where R, R′, R″, R″′,R″″, and R″″′
(Dithiomalonodiamides),	represent H, NH₂, or any organic functional
Bis(dithiomalonamides),	group wherein the number of carbon atoms
and Polydithiomalonamides	ranges from 0 to 40, optionally having
(S—S Bidentates,	halogen or polarizing or water-insolubilizing/
S—S Tridentates,	solubilizing groups attached. Ligand can also
S—S Tetradentates)	contain nonbinding N, O, S, or P atoms.
S Valence Stabilizer #8:	RR′—N—C(═S)—CR″R″′—C(═S)—R″″
2-Thioacylthioacetamides,	where R, R′, R″, R″′, and R″″ represent H,
Bis(2-thioacylthio-	NH₂, or any organic functional group
acetamides), and Poly(2-	wherein the number of carbon atoms ranges
thioacylthioacetamides)	from 0 to 40, optionally having halogen or
(S—S Bidentates,	polarizing or water-insolubilizing/
S—S Tridentates,	solubilizing groups attached. Ligand can also
S—S Tetradentates)	contain nonbinding N, O, S, or P atoms.
S Valence Stabilizer #9:	R—C(═S)—S—C(═S)—R′ where R and
Dithioacyl sulfides,	R′ represent H or any organic functional
Bis(dithioacyl sulfides),	group wherein the number of carbon atoms
and Poly(dithioacyl	ranges from 0 to 40, optionally having
sulfides) (S—S	halogen or polarizing or water-insolubilizing/
Bidentates, S—S	solubilizing groups attached. Ligand can also
Tridentates, S—S	contain nonbinding N, O, S, or P atoms.
Tetradentates)
S Valence Stabilizer #10:	RR′—N—C(═S)—S—C(═S)—N—R″R″′
Trithiodicarbonic Diamides,	where R, R′, R″, and R″′ represent H, NH₂
Bis(trithiodicarbonic	or any organic functional group wherein the
diamides), and Poly(tri-	number of carbon atoms ranges from 0 to 40,
thiodicarbonic diamides)	optionally having halogen or polarizing or
(S—S Bidentates,	water-insolubilizing/solubilizing groups
S—S Tridentates,	attached. Ligand can also contain nonbinding
S—S Tetradentates)	N, O, S, or P atoms.
S Valence Stabilizer #11:	R—S—C(═S)—S—C(═S)—S—R′ for
Pentathio-, Tetrathio-, or	pentathiodicarbonic acids, R—O—C(═S)—
Trithiodicarbonic Acids,	S—C(═S)—S—R′ for tetrathiodicarbonic
Bis(pentathio-, tetrathio-,	acids, and R—O—C(═S)—S—C(═S)—
or trithiodicarbonic acids),	O—R′ for pentathiodicarbonic acids,
Poly(pentathio-, tetrathio-,	where R and R′ represent H, NH₂or any
or trithiodicarbonic acids),	organic functional group wherein the number
and derivatives thereof	of carbon atoms ranges from 0 to 40,
(S—S Bidentates,	optionally having halogen or polarizing or
S—S Tridentates,	water-insolubilizing/solubilizing groups
S—S Tetradentates)	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
S Valence Stabilizer #12:	(R—O—)(R′—O—)P(═S)—P(═S)
Dithiohypophosphoric	(—O—R″)(—O—R″′); (R—O—)(R′—S—)
Acids, Bis(dithiohypo-	P(═S)—P(═S)(—S—R″)(—O—R″′);
phosphoric acids), and	or (R—S—)(R′—S—)P(═S)—P(═S)
Poly(dithiohypophosphoric	(—S—R″)(—S—R″′), where R, R′, R″, and
acids), and derivatives	R″′ represent H, NH₂or any organic
thereof (S—S Bidentates,	functional group wherein the number of
S—S Tridentates,	carbon atoms ranges from 0 to 40, optionally
S—S Tetradentates)	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S,
	or P atoms. Note: these ligands are not to be
	confused with hypophosphorous acid
	derivatives (hypophosphites) (R—O—)
	R″R″′P(═O) which are very reducing and
	therefore unacceptable for stabilization of
	high valence states in metal ions.
S Valence Stabilizer #13:	(RR′—N—)(R″R″′—N—)P(═S)(—N—
Dithiohypophosphoramides,	R″″R″″′)(—N—R″″″R″″″′), where R, R′,
Bis(dithiohypophosphor-	R″, R″′, and R″″, R″″′, R″″″, and R″″″′
amides), Poly(dithiohypo-	represent H, NH₂or any organic functional
phosphoramides) (S—S	group wherein the number of carbon atoms
Bidentates, S—S	ranges from 0 to 40, optionally having
Tridentates, S—S	halogen or polarizing or water-insolubilizing/
Tetradentates)	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
	Note: these ligands are not to be confused
	with hypophosphorous acid derivatives
	(hypophosphites) (R—O—)R″R″′P(═O)
	which are very reducing and therefore
	unacceptable for stabilization of high
	valence states in metal ions.
S Valence Stabilizer #14:	(R—O—)(R′—O—)P(═S)—NH—P(═S)
Dithioimidodiphosphoric	(—O—R″)(—O—R″′); (R—O—)(R′—S—)
Acids, Dithiohydrazidodi-	P(═S)—NH—P(═S )(—S—R″)(—O—
phosphoric Acids, Bis(di-	R″′); or (R—S—)(R′—S—)P(═S)—NH—
thioimidodiphosphoric	P(═S)(—S—R″)(—S—R″′) for dithio-
Acids), Bis(dithiohydra-	imidodiphosphoric acids, and —NH—NH—
zidodiphosphoric Acids),	derivatives for dithiohydrazidodiphosphoric
Poly(dithioimidodi-	acids, where R, R′, R″, and R″′ represent
phosphoric Acids), Poly(di-	H, NH₂or any organic functional group
thiohydrazidodiphosphoric	wherein the number of carbon atoms ranges
Acids), and derivatives	from 0 to 40, optionally having halogen or
thereof (S—S Bidentates,	polarizing or water-insolubilizing/
S—S Tridentates,	solubilizing groups attached. Ligand can also
S—S Tetradentates)	contain nonbinding N, O, S, or P atoms.
S Valence Stabilizer #15:	(RR′—N—)(R″R′″—N—)(═S)—NH—
Dithioimidodiphosphor-	P(═S)(—N—R″″R″″′)(—N—R″″″R″″″′)
amides, Dithiohydrazidodi-	for dithioimidophosphoramides, and
phosphoramides, Bis(di-	(RR ′—N—)(R″R″′—N—)P(═S)—NH—
thioimidodiphosphor-	NH—P(═S)(—N—R″″R″″′)
amides), Bis(dithiohydra-	(—N—R″″″R″″″′) for dithiohydrazidodi-
zidodiphosphoramides),	phosphoramides, where R, R′, R″, R″′, R″″,
Poly(dithioimidodiphos-	R″″′, R″″″, and R″″″′ represent H, NH₂or
phoramides), and Poly(di-	any organic functional group wherein the
thiohydrazidodiphosphor-	number of carbon atoms ranges from 0 to 40,
amides) (S—S Bidentates,	optionally having halogen or polarizing or
S—S Tridentates,	water-insolubilizing/solubilizing groups
S—S Tetradentates)	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
S Valence Stabilizer #16:	(RR′—N—)(R″R″′—N—)P(═S)—S—P(═S)(—N—
Dithiodiphosphoramides,	R″″R″″′)(—N—R″″″R″″″′), or (RR′—N—)
Bis(dithioiphosphor-	(R″R″′—N—)P(═S)—O—P(═S)
amides), and Poly(dithio-	(—N—R″″″R″″″′), where R, R′, R″, R″′,
diphosphoramides) (S—S	R″″, R″″′, R″″″, and R″″″′ represent H,
Bidentates, S—S	NH₂or any organic functional group wherein
Tridentates, S—S	the number of carbon atoms ranges from 0 to
Tetradentates)	40, optionally having halogen or polarizing
	or water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
S Valence Stabilizer #17:	(R—O—)(R ′—O—)P(═S)—O—
Dithiodiphosphoric Acids,	P(═S)(—O—R″)(—O—R″′);
Bis(dithioiphosphoric	(R—O—)(R ′—O—)P(═S)—S—
Acids), Poly(dithiodiphos-	P(═S)(—O—R″)(—O—R″′);
phoric Acids), and	(R—O—)(R ′—O—)P(═S)—O—
derivatives thereof	P(═S)(—O—R″)(—O—R″′);
(S—S Bidentates,	(R—O—)(R ′—O—)P(═S)—S—
S—S Tridentates,	P(═S)(—O—R″)(—O—R″′); or
S—S Tetradentates)	(R—S—)(R ′—O—)P(═S)—S—
	P(═S)(—O—R″)(—O—R″′);
	where R, R′, R″, R″′, R″″, R″″′, R″″″, and
	R″″″′represent H, NH₂or any organic
	functional group wherein the number of
	carbon atoms ranges from 0 to 40, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S,
	or P atoms.
S Valence Stabilizer #18:	(O═)P(—S—R)(—S—R′)(—S—R″) or
Trithiophosphoric Acids	(S═)P(—S—R)(—S—R′)(—O—R″),
(Phosphorotrithioic Acids),	where R, R′, and R″ represent H, NH₂or any
Bis(trithiophosphoric	organic functional group wherein the number
acids), Poly(trithiophos-	of carbon atoms ranges from 0 to 40,
phoric acids), and	optionally having halogen or polarizing or
derivatives thereof	water-insolubilizing/solubilizing groups
(S—S Bidentates,	attached. Ligand can also contain
S—S Tridentates,	nonbinding N, O, S, or P atoms.
S—S Tetradentates)
S Valence Stabilizer #19:	(O═)P(—S—R)(—S—R′)(—O—R″) or
Dithiophosphoric Acids	(S═)P(—S—R)(—O—R′)(—O—R″),
(Phosphorodithioic Acids),	where R, R′, and R″represent H, NH₂or any
Bis(dithiophosphoric acids),	organic functional group wherein the number
Poly(dithiophosphoric	of carbon atoms ranges from 0 to 40,
acids), and derivatives	optionally having halogen or polarizing or
thereof (S—S Bidentates,	water-insolubilizing/solubilizing groups
S—S Tridentates,	attached. Ligand can also contain nonbinding
S—S Tetradentates)	N, O, S, or P atoms.
S Valence Stabilizer #20:	(S═)P(—S—R)(—S—R′)(—S—R″), where
Tetrathiophosphoric Acids	R, R′, and R″ represent H, NH₂ or any
(Phosphorotetrathioic	organic functional group wherein the number
Acids), Bis(tetrathio-	of carbon atoms ranges from 0 to 40,
phosphoric acids),	optionally having halogen or polarizing or
Poly(tetrathiophosphoric	water-insolubilizing/solubilizing groups
acids), and derivatives	attached. Ligand can also contain nonbinding
thereof (S—S Bidentates,	N, O, S, or P atoms.
S—S Tridentates,
S—S Tetradentates)
S Valence Stabilizer #21:	(O═)P(—S—S—R)(—S—R′)(—S—R″) or
Phosphoro(dithioperoxo)di-	(S)P(—S—S—R)(—S—R′)(—O—R″),
thioic Acids, Bis[phos-	where R, R′, and R″represent H, NH₂or any
phoro(dithioperoxo)dithioic	organic functional group wherein the number
Acids], Poly[phosphoro(di-	of carbon atoms ranges from 0 to 40,
thioperoxo)dithioic Acids],	optionally having halogen or polarizing or
and derivatives thereof	water-insolubilizing/solubilizing groups
(S—S Bidentates,	attached. Ligand can also contain nonbinding
S—S Tridentates,	N, O, S, or P atoms.
S—S Tetradentates)
S Valence Stabilizer #22:	(O═)P(—S—S—R)(—S—R′)(—O—R″) or
Phosphoro(dithio-	(S═)P(—S—S—R)(—O—R′)(—O—R″),
peroxo)thioic Acids,	where R, R′, and R″represent H, NH₂or any
Bis[phosphoro(dithio-	organic functional group wherein the number
peroxo)thioic Acids],	of carbon atoms ranges from 0 to 40,
Poly[phosphoro(dithio-	optionally having halogen or polarizing or
peroxo)thioic Acids], water-insolubilizing/solubilizing groups
and derivatives thereof	attached. Ligand can also contain nonbinding
(S—S Bidentates,	N, O, S, or P atoms.
S—S Tridentates,
S—S Tetradentates)
S Valence Stabilizer #23:	(S═)P(—S—S—R)(—S—R′)(—S—R″),
Phosphoro(dithioper-	where R, R′, and R″ represent H, NH₂or any
oxo)trithioic Acids,	organic functional group wherein the number
Bis[phosphoro(dithio-	of carbon atoms ranges from 0 to 40,
peroxo)trithioic Acids],	optionally having halogen or polarizing or
Poly[phosphoro(dithio-	water-insolubilizing/solubilizing groups
peroxo)trithioic Acids],	attached. Ligand can also contain nonbinding
and derivatives thereof	N, O, S, or P atoms.
(S—S Bidentates,
S—S Tridentates,
S—S Tetradentates)
S Valence Stabilizer #24:	R—CR′(—SH)—CH₂—C(═S)—R″, where
Beta-Mercaptothioketones,	R, R′, and R″ represent H, NH₂or any
Beta-Mercaptothio-	organic functional group wherein the number
aldehydes, Bis(beta-	of carbon atoms ranges from 0 to 40,
mercaptothioketones),	optionally having halogen or polarizing or
Bis(beta-mercaptothio-	water-insolubilizing/solubilizing groups
aldehydes), Poly(beta-	attached. Ligand can also contain nonbinding
mercaptothioketones),	N, O, S, or P atoms.
and Poly(beta-
mercaptothioaldehydes)
(S—S Bidentates,
S—S Tridentates,
S—S Tetradentates)
S Valence Stabilizer #25:	RR′—N—CH(—SH)—NR″—C(═S)—
N-(Aminomethylthiol)thio-	NR″′R″″, where R, R′, R″, R″′, and R″″
ureas [N-(Aminomercapto-	represent H, NH₂or any organic functional
methyl)thioureas], Bis[N-	group wherein the number of carbon atoms
(aminomethylthiol)thio-	ranges from 0 to 40, optionally having
ureas], and Poly[N-(amino-	halogen or polarizing or water-insolubilizing/
methylthiol)thioureas]	solubilizing groups attached. Ligand can also
(S—S Bidentates,	contain nonbinding N, O, S, or P atoms.
S—S Tridentates,
S—S Tetradentates)
S Valence Stabilizer #26:	RR′—N—C(═S)—C(═S)—N—R″R″′,
Dithiooxamides,	where R, R′, and R″, and R″′ represent H,
Bis(dithiooxamides),	NH₂or any organic functional group wherein
Poly(dithiooxamides)	the number of carbon atoms ranges from 0
(S—S Bidentates,	to 40, optionally having halogen or
S—S Tridentates,	polarizing or water-insolubilizing/
S—S Tetradentates)	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
S Valence Stabilizer #27:	RR′—C═C(—S⁻)(—S⁻), where R and R′
1,1-Dithiolates, Bis(1,1-	represent H, NH₂or any organic functional
dithiolates), and	group wherein the number of carbon atoms
Poly(1,1-dithiolates)	ranges from 0 to 40, optionally having
(S—S Bidentates and	halogen or polarizing or water-insolubilizing/
S—S Tetradentates)	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
S Valence Stabilizer #28:	R—C(═S)(—S—R′) for dithiomono-
Dithiomonocarboxylic	carboxylic acids, and (R—S—)(S═)C—
Acids, Tri- and Tetrathio-	R′—C(═S)(—S—R″) for tri- and tetra-
dicarboxylic Acids,	thiodicarboxylic acids, where R, R′, and R″
Bis(dithiomonocarboxylic	represent H, NH₂or any organic functional
Acids), Bis(tri- and tetra-	group wherein the number of carbon atoms
thiodicarboxylic acids),	ranges from 0 to 40, optionally having
Poly(dithiomonocarboxylic	halogen and or polarizing or water-
acids), Poly(tri- and	insolubilizing/solubilizing groups attached.
tetrathiodicarboxylic	Ligand can also contain nonbinding N, O, S,
acids), derivatives thereof	or P atoms.
(S—S Bidentates and
S—S Tetradentates)
S Valence Stabilizer #29:	R—C(═S)(—S—S—R′) for perthiomono-
Perthiomonocarboxylic	carboxylic acids, and (R—S—S—)(S═)C—
Acids, Perthiodicarboxylic	R′—C(═S)(—S—S—R″) for perthiodi-
Acids, Bis(perthiomono-	carboxylic acids, where R, R′, and R″
carboxylic acids),	represent H, NH₂or any organic functional
Bis(perthiodicarboxylic	group wherein the number of carbon atoms
acids), Poly(perthiomono-	ranges from 0 to 40, optionally having
carboxylic acids),	halogen or polarizing or water-
Poly(perthiodicarboxylic	insolubilizing/solubilizing groups attached.
acids), and derivatives	Ligand can also contain nonbinding N, O, S,
thereof (S—S Bidentates	or P atoms.
and S—S Tetradentates)
S Valence Stabilizer #30:	R—S—C(═S)—O—R′ or
Dithiocarbonates,	R—S—C(═O)—S—R′ for dithiocarbonates,
Trithiocarbonates,	R—S—C(═S)—S—R′ for trithiocarbonates,
Perthiocarbonates,	and R—S—S—C(═S)—S—R′ for perthio-
Bis(dithiocarbonates),	carbonates, where R, and R′ represent H,
Bis(trithiocarbonates), and	NH₂or any organic functional group wherein
Bis(perthiocarbonates)	the number of carbon atoms ranges from 0 to
(S—S Bidentates and	40, optionally having halogen or polarizing
S—S Tetradentates)	or water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
S Valence Stabilizer #31:	RR′N^{+ ═C(SH)(SH), where R and R′ represent}
Dithiocarbamates,	H, OH, SH, OR″ (R″═C₁-C₃₀alkyl or
Bis(dithiocarbamates),	aryl), SR″ (R″═C₁-C₃₀alkyl or aryl),
and Poly(dithiocarbamates)	NH₂or any organic functional group wherein
(including N-hydroxydi-	the number of carbon atoms ranges from 0 to
thiocarbamates and N-	40, optionally having halogen or polarizing
mercaptodithiocarbamates)	or water-insolubilizing/solubilizing groups
(S—S Bidentates,	attached. Ligand can also contain nonbinding
S—S Tridentates, and	N, O, S, or P atoms.
S—S Tetradentates)
S Valence Stabilizer #32:	RR′N—NR″—C(═S)(SH), where R and R′
Dithiocarbazates	represent H, NH₂or any organic functional
(Dithiocarbazides),	group wherein the number of carbon atoms
Bis(dithiocarbazates), and	ranges from 0 to 40, optionally having
Poly(dithiocarbazates)	halogen or polarizing or water-
(S—S Bidentates,	insolubilizing/solubilizing groups
S—S Tridentates, and	attached. Ligand can also contain nonbinding
S—S Tetradentates; or	N, O, S, or P atoms.
possibly N—S Bidentates,
N—S Tridentates, and
N—S Tetradentates)
S Valence Stabilizer #33:	Thiocyanates bound directly to the high
Thiocyanate ligands	valence metal ion.
(S Monodentates)
O Valence Stabilizer #1:	RR′—N—C(═O)—NR″—C(═O)—
Biurets (Imidodicarbonic	NR″′R″″ for biurets, and RR′—N—
Diamides), Isobiurets,	C(═O)—NR″—NH—C(═O)—NR″′R″″
Biureas, Triurets,	for biureas, where R, R′, R″, R″′, and R′″′
Triureas, Bis(biurets),	represent H, NH₂, or any organic functional
Bis(isobiurets),	group wherein the number of carbon atoms
Bis(biureas), Poly(biurets),	ranges from 0 to 40, optionally having
Poly(isobiurets),	halogen or polarizing or water-
and Poly(biureas)	insolubilizing/solubilizing groups
(O—O Bidentates,	attached. Ligand can also contain nonbinding
O—O Tridentates,	N, O, S, or P atoms.
O—O Tetradentates)
O Valence Stabilizer #2:	RR′—N—C(═O)—NR″—C(═O)—R″′
Acylureas, Aroylureas,	where R, R′, R″, and R″′ represent H, NH₂,
Bis(acylureas),	or any organic functional group wherein the
Bis(aroylureas),	number of carbon atoms ranges from 0 to 40,
Poly(acylureas), and	optionally having halogen or polarizing or
Poly(aroylureas)	water-insolubilizing/solubilizing groups
(O—O Bidentates,	attached. Ligand can also contain nonbinding
O—O Tridentates,	N, O, S, or P atoms.
O—O Tetradentates)
O Valence Stabilizer #3:	RC(═O)—NR′—C(═O)—R″ for
Imidodialdehydes,	imidodialdehydes, and RC(═O)—NR —
Hydrazidodialdehydes	NH—C(═O)—R″ for hydrazidodialdehydes
(Acyl hydrazides),	(acyl hydrazides), where R, R′, and R″
Bis(imidodialdehydes),	represent H, NH₂, or any organic functional
Bis(hydrazidodialdehydes),	group wherein the number of carbon atoms
Poly(imidodialdehydes),	ranges from 0 to 40, optionally having
and Poly(hydrazidodi-	halogen or polarizing or water-
aldehydes) (O—O	insolubilizing/solubilizing groups attached.
Bidentates, O—O	Ligand can also contain nonbinding N, O, S,
Tridentates, O—O	or P atoms.
Tetradentates)
O Valence Stabilizer #4:	R—O—C(═O)—NR′—C(═O)—O—R″ for
Imidodicarbonic acids,	imidodicarbonic acids, and R—O—
Hydrazidodicarbonic acids,	C(═O)—NR′—NH—C(═O)—O—R″ for
Bis(imidodicarbonic acids),	hydrazidodicarbonic acids, where R, R′, and
Bis(hydrazidodicarbonic	R″ represent H, NH₂, or any organic
acids), Poly(imidodi-	functional group wherein the number of
carbonic acids),	carbon atoms ranges from 0 to 40, optionally
Poly(hydrazidodicarbonic	having halogen or polarizing or water-
acids) and derivatives	insolubilizing/solubilizing groups attached.
thereof (O—O Bidentates,	Ligand can also contain nonbinding N, O, S,
O—O Tridentates,	or P atoms.
O—O Tetradentates)
O Valence Stabilizer #5:	RR′—N—S(═O)(═O)—NR″—
Imidodisulfamic Acid,	S(═O)(═O)—NR′″R″″ for imidodisulfamic
Imidodisulfuric Acid,	acid, and R—O—S(═O)(═O)—NR′—
Bis(Imidodisulfamic Acid),	S(═O)(═O)—OR″ for imidosulfuric acid,
Bis(Imidodisulfuric Acid),	where R, R′, and R″ represent H, NH₂, or
Poly(Imidodisulfamic	any organic functional group wherein the
Acid), and Poly(Imido-	number of carbon atoms ranges from 0 to 40,
disulfuric Acid) and	optionally having halogen or polarizing or
derivatives thereof	water-insolubilizing/solubilizing groups
(O—O Bidentates,	attached. Ligand can also contain nonbinding
O—O Tridentates,	N, O, S, or P atoms.
O—O Tetradentates)
O Valence Stabilizer #6:	R—C(═O)—CR′R″—C(═O)—R″′ where
1,3-Diketones (Beta-	R, R′, R″, and R″′ represent H, NH₂, or any
Diketonates), 1,3,5-	organic functional group wherein the number
Triketones, Bis(1,3-	of carbon atoms ranges from 0 to 40,
Diketones), and Poly(1,3-	optionally having halogen or polarizing or
Diketones), all with a	water-insolubilizing/solubilizing groups
Molecular Weight Greater	attached. Ligand can also contain nonbinding
than 125 (O—O Bidentates,	N, O, S, or P atoms. If these ligands exhibit
O—O Tridentates,	a molecular weight less than or equal to 125,
O—O Tetradentates)	the solubility of the resultant Mn⁺³-
	diketonate complex will be too high.
O Valence Stabilizer #7:	R—C(═O)—C(═O)—R′ where R and R′
1,2-Diketones (Alpha-	represent H, NH₂, or any organic functional
Diketonates), 1,2,3-	group wherein the number of carbon atoms
Triketones, Tropolonates,	ranges from 0 to 40, optionally having
ortho-Quinones,	halogen or polarizing or water-insolubilizing/
Bis(1,2-Diketones), and	solubilizing groups attached. Ligand can also
Poly(1,2-Diketones), all	contain nonbinding N, O, S, or P atoms. If
with a Molecular Weight	these ligands exhibit a molecular weight less
Greater than 100	than or equal to 100, the solubility of the
(O—O Bidentates,	resultant Mn⁺³-diketonate complex will be
O—O Tridentates,	too high.
O—O Tetradentates)
O Valence Stabilizer #8:	RR′—N—C(═)—CR″R″′—C(═O)—N—
Malonamides	R″″R″″′ where R, R′, R″, R″′,R″″, and R″″′
(Malonodiamides),	represent H, NH₂, or any organic functional
Bis(malonamides), and	group wherein the number of carbon atoms
Polymalonamides	ranges from 0 to 40, optionally having
(O—O Bidentates,	halogen or polarizing or water-
O—O Tridentates,	insolubilizing/solubilizing groups attached.
O—O Tetradentates)	Ligand can also contain nonbinding N,
	O, S, or P atoms.
O Valence Stabilizer #9:	RR′—N—C(═O)—CR″R″′—C(═O)—R″″
2-Acylacetamides,	where R, R′, R″, R″′, and R″″ represent H,
Bis(2-acylacetamides),	NH₂, or any organic functional group
and Poly(2-acylacetamides)	wherein the number of carbon atoms ranges
(O—O Bidentates,	from 0 to 40, optionally having halogen or
O—O Tridentates,	polarizing or water-insolubilizing/
O—O Tetradentates)	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
O Valence Stabilizer #10:	RR′—N—C(═O)—S—C(═O)—N—R″R″′
Monothiodicarbonic	where R, R′, R″, and R″′ represent H, NH₂or
Diamides,	any organic functional group wherein the
Bis(monothiodicarbonic	number of carbon atoms ranges from 0 to 40,
diamides), and	optionally having halogen or polarizing or
Poly(monothiodicarbonic	water-insolubilizing/solubilizing groups
diamides) (O—O	attached. Ligand can also contain nonbinding
Bidentates, O—O	N, O, S, or P atoms.
Tridentates, O—O
Tetradentates)
O Valence Stabilizer #11:	R—O—C(═O)—S—C(═O)—O—R′,
Monothiodicarbonic Acids,	where R and R′ represent H, NH₂or any
Bis(monothiodicarbonic	organic functional group wherein the number
acids), Poly(monothiodi-	of carbon atoms ranges from 0 to 40,
carbonic acids), and	optionally having halogen or polarizing or
derivatives thereof	water-insolubilizing/solubilizing groups
(O—O Bidentates,	attached. Ligand can also contain nonbinding
O—O Tridentates,	N, O, S, or P atoms.
O—O Tetradentates)
O Valence Stabilizer #12:	R—O—S(═O)(═O)—S—S(═O)—O—R′
Trithionic acid,	where R and R′ represent H, NH₂or any
Bis(trithionic acid),	organic and derivatives functional group wherein the
Poly(trithionic acid),	number of carbon atoms ranges from 0 to 40,
thereof (O—O Bidentates,	optionally having halogen or polarizing or
O—O Tridentates,	water-insolubilizing/solubilizing groups
O—O Tetradentates)	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
O Valence Stabilizer #13:	(R—O—)(R′—O—)P(═O)—
Hypophosphoric Acids,	P(═O) (—O—R″)(—O—R′″), where R,
Bis(hypophosphoric acids),	R′, R″, and R″′ represent H, NH₂or any
and Poly(hypophosphoric	organic functional group wherein the number
acids), and derivatives	of carbon atoms ranges from 0 to 40,
thereof (O—O Bidentates,	optionally having halogen or polarizing or
O—O Tridentates,	water-insolubilizing/solubilizing groups
O—O Tetradentates)	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms. Note: these ligands are
	not to be confused with hypophosphorous acid
	derivatives (hypophosphites)
	(R—O—)R″R″′P(═O) which are very
	reducing and therefore unacceptable for
	stabilization of high valence states in
	metal ions.
O Valence Stabilizer #14:	(RR′—N—)(RR″R′″—N—)P(═O)—
Hypophosphoramides,	P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′),
Bis(hypophosphoramides),	where R, R′, R″, R″′, R″″, R″″′, R″″″, and
and Poly(hypophosphor-	R″″″′represent H, NH₂or any organic
amides) (Q—O Bidentates,	functional group wherein the number of
O—O Tridentates,	carbon atoms ranges from 0 to 40, optionally
O—O Tetradentates)	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O,
	S, or P atoms. Note: these ligands are not to
	be confused with hypophosphorous acid
	derivatives (hypophosphites)
	(R—O—)R″R″′P(═O) which are very
	reducing and therefore unacceptable for
	stabilization of high valence states in
	metal ions.
O Valence Stabilizer #15:	(R—O—)(R′—O—)P(═O)—NH—
Imidodiphosphoric Acids,	P(═O)(—O—R″)(—O)—R″′) for
Hydrazidodiphosphoric	imidodiphosphoric acids, and (R—O—)(R′—
Acids, Bis(imidodiphos-	O—)P(═O)—NH—NH—P(═O)(—O—R″)
phoric Acids), Bis(hydra-	(—O—R″′) for hydrazidodiphosphoric
zidodiphosphoric Acids),	acids; where R, R′, R″, and R″′ represent H,
Poly(imidodiphosphoric	NH₂ or any organic functional group
Acids), Poly(hydra-	wherein the number of carbon atoms ranges
zidodiphosphoric Acids),	from 0 to 40, optionally having halogen or
and derivatives thereof	polarizing or water-insolubilizing/
(O—O Bidentates,	solubilizing groups attached. Ligand can also
O—O Tridentates,	contain nonbinding N, O, S, or P atoms.
O—O Tetradentates)
O Valence Stabilizer #16:	(RR′—N—)(R″R″′—N—)P(═O)—NH—
Imidodiphosphoramides,	P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′)
Hydrazidodiphos-	for imidodiphosphoramides, and
phoramides, Bis(imidodi-	—NH—NH— derivatives for hydrazidodi-
phosphoramides),	phosphoramides, where R, R′, R″, R″′, R″″,
Bis(hydrazidodi-	R″″′, R″′″′, and R″″″′ represent H, NH₂or
phosphoramides),	any organic functional group wherein the
Poly(imidodiphos-	number of carbon atoms ranges from 0 to 40,
phoramides), and	optionally having halogen or polarizing or
Poly(hydrazidodi-	water-insolubilizing/solubilizing groups
phosphoramides)	attached. Ligand can also contain nonbinding
(O—O Bidentates,	N, O, S, or P atoms.
O—O Tridentates,
O—O Tetradentates)
O Valence Stabilizer #17:	(RR′—N—)(R″R″′—N—)PQ═O)—O—
Diphosphoramides,	P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′),
Bis(diphosphoramides), and	where R, R′, R″, R″′, R″″, R″″′, R″″″, and
Poly(diphosphoramides)	R″″″′ represent H, NH₂or any organic
(O—O Bidentates,	functional group wherein the number of
O—O Tridentates,	carbon atoms ranges from 0 to 40, optionally
O—O Tetradentates)	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N,
	O, S, or P atoms.
O Valence Stabilizer #18:	R—CR′(—OH)—CH2—C(═O)—R″,
Beta-Hydroxyketones,	where R, R′, and R″ represent H, NH₂or
Beta-Hydroxyaldehydes,	any organic functional group wherein the
Bis(beta-hydroxyketones),	number of carbon atoms ranges from 0 to 40,
Bis(beta-	optionally having halogen or polarizing or
hydroxyaldehydes),	water-insolubilizing/solubilizing groups
Poly(beta-hydroxyketones),	attached. Ligand can also contain nonbinding
and Poly(beta-	N, O, S, or P atoms.
hydroxyaldehydes)
(O—O Bidentates,
O—O Tridentates,
O—O Tetradentates)
O Valence Stabilizer #19:	RR′—N—CH(—OH)—NR″—C(═O)—
N-(Aminomethylol)ureas	NR″′R″″, where R, R′, R″, R″′, and R″″
[N-(Aminohydroxy-	represent H, NH₂or any organic functional
methyl)ureas], Bis[N-	group wherein the number of carbon atoms
(aminomethylol)ureas],	ranges from 0 to 40, optionally having
and Poly[N-(amino-	halogen or polarizing or water-insolubilizing/
methylol)ureas]	solubilizing groups attached. Ligand can also
(O—O Bidentates,	contain nonbinding N, O, S, or P atoms.
O—O Tridentates,
O—O Tetradentates)
O Valence Stabilizer #20:	RR′—N—C(═O)—C(═O)—N—R″R″′,
Oxamides, Bis(oxamides),	where R, R′, R″, and R″′ represent H, NH₂or
and Poly(oxamides)	any organic functional group wherein the
(O—O Bidentates,	number of carbon atoms ranges from 0 to 40,
O—O Tridentates,	optionally having halogen or polarizing or
O—O Tetradentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
O Valence Stabilizer #21:	—C(—OH)═C(—OH)—, where the two
Squaric Acids and	carbon atoms supporting the hydroxy groups
derivatives thereof	are included within a cyclic hydrocarbon
(O—O Bidentates)	moiety, optionally having halogen or
	polarizing or water-insolubilizing/
	solubilizing groups attached. Ligand can
	also contain nonbinding N, O, S, or P atoms.
O Valence Stabilizer #22:	(R—O—)(O═)C—R′—C(═O)(—O—R″),
Dicarboxylic Acids,	where R, R′,and R″ represent H, NH₂ or
Bis(dicarboxylic acids),	any organic functional group wherein the
Poly(dicarboxylic acids),	number of carbon atoms ranges from 0 to 40,
and derivatives thereof	optionally having halogen or polarizing or
(O—O Bidentates and	water-insolubilizing/solubilizing groups
O—O Tetradentates)	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
O Valence Stabilizer #23:	RR′N⁺═C(OH)(OH), where R and R′
Carbamates,	represent H, OH, SH, OR″ (R″═C₁-C₃₀
Bis(carbamates), and	alkyl or aryl), SR″ (R″═C₁-C₃₀alkyl
Poly(carbamates)	or aryl), NH₂or any organic functional
(including N-	group wherein the number of carbon atoms
hydroxycarbamates and	ranges from 0 to 40, optionally having
N-mercaptocarbamates)	halogen or polarizing or water-insolubilizing/
(O—O Bidentates,	solubilizing groups attached. Ligand can also
O—O Tridentates, and	contain nonbinding N, O, S, or P atoms.
O—O Tetradentates)
O Valence Stabilizer #24:	RN═C(OH)(OH), where R represents H,
Carbimates,	NH₂or any organic functional group wherein
Bis(carbimates), and	the number of carbon atoms ranges from 0 to
Poly(carbimates)	40, optionally having halogen or polarizing
(O—O Bidentates,	or water-insolubilizing/solubilizing groups
O—O Tridentates, an	attached. Ligand can also contain nonbinding
O—O Tetradentates)	N, O, S, or P atoms.
O Valence Stabilizer #25:	Cyanates bound directly to the high valence
Cyanate ligands	metal ion.
(O Monodentates)
N—S Valence	RR′—N—C(═NH)—S—S—C(═NH)—
Stabilizer #1:	NR″R″′, where R, R′, R″, and R″′ represent
Diformamidine Disulfides	H, NH₂, or any organic functional group
(Thioperoxydicarbonimidic	wherein the number of carbon atoms ranges
Diamides or Dihydrazides),	from 0 to 40, optionally having halogen or
Thioperoxytricarbonimidic	polarizing or water-insolubilizing/
Diamides or Dihydrazides,	solubilizing groups attached. Ligand can also
Thioperoxytetra-	contain nonbinding N, O, S, or P atoms.
carbonimidic Diamides or
Dihydrazides,
Bis(diformamidine
disulfides), and
Poly(diformamidine
disulfides)
(N—S Bidentates,
N—S Tridentates,
N—S Tetradentates)
N—S Valence	RR′—N—C(═NH)—S—CS—NR″R″′,
Stabilizer #2:	where R, R′, R″, and R″′ represent H, NH₂or
S-Amidinodithio-	any organic functional group wherein the
carbamates, Bis(S-amidino-	number of carbon atoms ranges from 0 to 40,
dithiocarbamates), and	optionally having halogen or polarizing or
Poly(S- amidinodithio-	water-insolubilizing/solubilizing groups
carbamates) (N—S	attached. Ligand can also contain nonbinding
Bidentates and	N, O, S, or P atoms.
N—S Tetradentates)
N—S Valence	RR′—N—C(═NH)—O—CS—NR″R″′,
Stabilizer #3:	where R, R′, R″, and R″′ represent H, NH₂or
O-Amidinothiocarbamates,	any organic functional group wherein the
Bis(O-amidinothio-	number of carbon atoms ranges from 0 to 40,
carbamates), and Poly(O-	optionally having halogen or polarizing or
amidinothiocarbamates)	water-insolubilizing/solubilizing groups
(N—S Bidentates and	attached. Ligand can also contain nonbinding
N—S Tetradentates)	N, O, S, or P atoms.
N—S Valence	RR′—N—C(═NH)—S—S—CS—NR″R″′,
Stabilizer #4:	where R, R′, R″, and R″′ represent H, NH₂or
S-Amidinoperoxythio-	any organic functional group wherein the
carbamates, Bis(S-amidino-	number of carbon atoms ranges from 0 to 40,
peroxythiocarbamates), and	optionally having halogen or polarizing or
Poly(S-amidinoperoxythio-	water-insolubilizing/solubilizing groups
carbamates) (N—S	attached. Ligand can also contain nonbinding
Bidentates and N—S	N, O, S, or P atoms.
Tetradentates)
N—S Valence	(NH═)P(—SR)(—OR′)(—OR″) for
Stabilizer #5:	phosphorimidothioic acid, (NH═)P(═SR)
Phosphorimidothioic Acid;	(═SR′)(OR″) for phosphorimidodithioic
Phosphorimidodithioic	acid, (NH═)P(—SR)(—SR′)(—SR″) for
Acid; Phosphorimidotri-	phosphorimidotrithioic acid, where R, R′,
thiole Acid; Bis(Phos-	and R″ represent H, NH₂or any organic
phorimidothioic Acid);	functional group wherein the number of
Bis(Phosphorimidodithioic	carbon atoms ranges from 0 to 40, optionally
Acid); Bis(Phosphorimido-	having halogen or polarizing or water-
trithioic Acid); Poly(Phos-	insolubilizing/solubilizing groups attached.
phorimidothioic Acid);	Ligand can also contain nonbinding N,
Poly(Phosphorimidodithioic	O, S, or P atoms.
Acid); Poly(Phosphor-
imidotrithioic Acid); and
derivatives thereof
(N—S Bidentates
and N—S Tetradentates)
N—S Valence	(S═)P(—NRR′)(—NR″R″′)(—NR″″R″″′),
Stabilizer #6:	where R, R′, R″, R″′, R″″, and R″″′ represent
Phosphorothioic Triamides,	H, NH₂or any organic functional group
Bis(phosphorothioic	wherein the number of carbon atoms ranges
triamides), and Poly(phos-	from 0 to 40, optionally having halogen or
phorothioic triamides)	polarizing or water-insolubilizing/
(N—S Bidentates	solubilizing groups attached. Ligand can also
and N—S Tetradentates)	contain nonbinding N, O, S, or P atoms.
N—S Valence	(S═)P(—NRR′)(—SR″)(—SR″′) for
Stabilizer #7:	phosphoramidotrithioic acid, and
Phosphoramidotrithioic	(S═)P(—NRR ′)(—NR″R″′)(—SR″″) for
Acid, Phosphorodiamido-	phosphorodiamidodithioic acid, where R, R′,
dithioic Acid,	R″, R″′, and R″″represent H, NH₂or any
Bis(phosphoramido-	organic functional group wherein the number
trithioic acid),	of carbon atoms ranges from 0 to 40,
Bis(phosphorodiamido-	optionally having halogen or polarizing or
dithioic acid),	water-insolubilizing/solubilizing groups
poly(phosphoramido-	attached. Ligand can also contain nonbinding
trithioic acid),	N, O, S, or P atoms.
poly(phosphorodiamido-
dithioic acid), and
derivatives thereof
(N—S Bidentates
and N—S Tetradentates)
N—S Valence	(O═)P(—NRR′)(—SR″)(—OR″′) or
Stabilizer #8:	(S═)P(—NRR′)(—OR″)(—OR″′) for
Phosphoramidothioic Acid,	phosphoramidothioic acid;
Phosphoramidodithioic	(O═)P(—NRR′)(—SR″)(—SR″′) or
Acid, Phosphorodi-	(S═)P(—NRR′)(—SR″)(—OR″′) for
amidothioic Acid,	phosphoramidodithioic acid;
Bis(Phosphoramido-	(O═)P(—NRR′NR″R″′)(—SR″″) or
thioic Acid),	(S═)P(—NRR′)(—NR″R″′)(—OR″″) for
Bis(Phosphoramido-	phosphorodiamidothioic acid, where R, R′,
dithioic Acid),	R″, R″′, and R″″represent H, NH₂or any
Bis(Phosphorodi-	organic functional group wherein the number
amidothioic Acid),	of carbon atoms ranges from 0 to 40,
Poly(Phosphoramido-	optionally having halogen or polarizing or
thioic Acid),	water-insolubilizing/solubilizing groups
Poly(Phosphoramido-	attached. Ligand can also contain nonbinding
dithioic Acid), and	N, O, S, or P atoms.
Poly(Phosphorodi-
amidothioic Acid)
(N—S Bidentates
and N—S Tetradentates)
N—S Valence	R′—C(═S)—N═C(—R)(—NHR″), where
Stabilizer #9:	R is an aromatic derivative (i.e. —C₆H₅),
N-Thioacyl	and R′and R″ represent H, NH₂, or any
7-Aminobenzylidenimines	organic functional group wherein the number
(N—S Bidentates or	of carbon atoms ranges from 0 to 40,
N—S Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—S Valence	R—C(═S)—NR′—OH or
Stabilizer #10:	R—C(—SH)═N—OH, where R and R′
Thiohydroxamates	represent H, NH₂, or any organic functional
(Thiohydroxylamines),	group wherein the number of carbon atoms
Bis(thiohydroxamates), and	ranges from 0 to 40, optionally having
Poly(thiohydroxamates)	halogen or polarizing or water-insolubilizing/
(N—S Bidentates,	solubilizing groups attached. Ligand can also
N—S Tetradentates,	contain nonbinding N, O, S, or P atoms.
and N—S Hexadentates)
N—S Valence	R—CH(—NHR′)—C(═S)(—OH) or
Stabilizer #11:	R—CH(—NHR′)—C(═5)(—SH) for
Alpha- or ortho-	aminothiocarboxylic acids, and
Aminothiocarboxylic	(HO—)(S═)C—CH(—NHR)—R′—CH(—
Acids, and alpha- or ortho-	NHR″)—C(═S)(—OH) or (HS—)(S═)C—
Aminothiodicarboxylic	CH(—NHR)—R′—CH(—NHR″)—
Acids, and derivatives	C(═S)(—SH) for aminothiodicarboxylic
thereof (N—S Bidentates,	acids, where R, R′, and R″represent any
N—S Tridentates,	organic functional group wherein the
and N—S Tetradentates)	number of carbon atoms ranges from 1 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—S Valence	RR′—N—C(═S)—NR″—N═CR″′R″″,
Stabilizer #12:	where R, R′, R″, R″′, and R″″ represent H,
Thiosemicarbazones,	or any organic functional group wherein the
Bis(thiosemicarbazones),	number of carbon atoms ranges from 0 to 40,
and Poly(thiosemi-	optionally having halogen or polarizing or
carbazones) (N—S	water-insolubilizing/solubilizing groups
Bidentates, N—S	attached. Ligand can also contain nonbinding
Tetradentates, and	N, O, S, or P atoms.
N—S Hexadentates)
N—S Valence	R—C(═S)—NR′—N═CR″R″′, where R,
Stabilizer #13:	R′, R″, and R″′ represent H, or any organic
Thioacyl hydrazones,	functional group wherein the number of
Bis(thioacyl hydrazones),	carbon atoms ranges from 0 to 40, optionally
and Poly(thioacyl	having halogen or polarizing or water-
hydrazones)	insolubilizing/solubilizing groups attached.
(N—S Bidentates,	Ligand can also contain nonbinding N, O,
N—S Tetradentates,	S, or P atoms.
and N—S Hexadentates)
N—S Valence	R—N═N—C(═S)—NR′—NR″R″′, where
Stabilizer #14:	R, R′, R″, R″′ represent H, or any organic
Thiocarbazones	functional group wherein the number of
(Diazenecarbothioic and	carbon atoms ranges from 0 to 40, optionally
hydrazides),	having halogen or polarizing or water-
Bis(thiocarbazones), and	insolubilizing/solubilizing groups attached.
Poly(thiocarbazones)	Ligand can also contain nonbinding N, O,
(N—S Bidentates,	S, or P atoms.
N—S Tetradentates,
and N—S Hexadentates)
N—S Valence	R—N═N—R′ for azo compounds,
Stabilizer #15:	R—N═N—NH—R′ for triazenes, where R,
Azo compounds including	and R′ represent H or any organic functional
triazenes with thiol or	group wherein the number of carbon atoms
mercapto or thiocarbonyl	ranges from 0 to 40, optionally having
substitution at the ortho-	halogen or polarizing or water-insolubilizing/
(for aryl) or alpha- or beta-	solubilizing groups attached. (Must include
(for alkyl) positions,	ortho-thio, mercapto, or thiocarbonyl
Bis[o-(HS-) or alpha-	substituted aryl azo compounds, and alpha-
or beta-(HS-)azo	or beta-thio, mercapto, or thiocarbonyl alkyl
compounds], or	azo compounds.) Ligand can also contain
Poly[o-(HS-) or alpha-	nonbinding N, O, S, or P atoms.
or beta-(HS-)azo
compounds)
(N—S Bidentates,
N—S Tridentates,
N—S Tetradentates,
or N—S Hexadentates)
N—S Valence	R—N═N—C(═S)—N′R′R″
Stabilizer #16:	for diazeneformothioamides, and
Diazeneformothioamides,	R—N═N—CR′R″—C(═S)—NR″′R″″
Diazeneacetothioamides,	for diazeneacetothioamides, where R, R′, R″,
Bis(diazene-	R″′, and R″″ represent H, NH₂, or any
formothioamides),	organic functional group wherein the number
Bis(diazene-	of carbon atoms ranges from 0 to 40,
acetothioamides),	optionally having halogen or polarizing or
Poly(diazene-	water-insolubilizing/solubilizing groups
formothioamides), and	attached. Ligand can also contain nonbinding
Poly(diazene-	N, O, S, or P atoms.
acetothioamides)
(N—S Bidentates,
N—S Tetradentates,
and N—S Hexadentates)
N—S Valence	R—N═N—C(═S)—O—R′ or
Stabilizer #17:	R—N═N—CR′R″—C(═S)—O—R″′
Diazenecarbothioic acids,	for diazenecarbothioic acids, and
Diazenecarbodithioic acids,	R—N═N—C(═S)—S—R′ or
Bis(diazene-	R—N═N—CR′R″—C(═′S)—S—R″′
carbothioic acids),	for diazenecarbodithoic acids, where R, R′,
Bis(diazene-	R″, and R″′ represent H, NH₂, or any
carbodithioic acids),	organic functional group wherein the number
Poly(diazene-	of carbon atoms ranges from 0 to 40,
carbothioic acids),	optionally having halogen or polarizing or
Poly(diazene-	water-insolubilizing/solubilizing groups
carbodithioic acids) and	attached. Ligand can also contain nonbinding
derivatives thereof	N, O, S, or P atoms.
(N—S Bidentates,
N—S Tetradentates,
N—S Hexadentates)
N—S Valence	R—N═N—C(═S)—R′for
Stabilizer #18:	diazeneformothioaldehydes, and
Diazeneformo-	R—N═N—CR′R″—C(═S)—R″′ for
thioaldehydes,	diazeneacetothioaldehydes, where R, R′, R″,
Diazeneaceto-	and R″′ represent H, NH₂, or any organic
thioaldehydes,	functional group wherein the number of
Bis(diazeneformo-	carbon atoms ranges from 0 to 40, optionally
thioaldehydes),	having halogen or polarizing or water-
Bis(diazeneaceto-	insolubilizing/solubilizing groups attached.
thioaldehydes),	Ligand can also contain nonbinding N, O, S,
Poly(diazeneformo-	or P atoms.
thioaldehydes), and
Poly(diazeneaceto-
thioaldehydes)
(N—S Bidentates,
N—S Tetradentates
and N—S Hexadentates)
N—S Valence	RR′—N—C(═S)—N═N—C(═S)—
Stabilizer #19:	NR″R′″ or RR′—N—C(═S)—
Diazenediformothioamides,	N═N—C(═O)—NR″R″′ for
Diazenediacetothioamides,	diazenediformothioamides, and RR′—N—
Bis(diazenedi-	C(═S)—CR″R″′—N═N—CR″″R″″′—
formothioamides),	C(═S)—NR″″″R″″″′ or
Bis(diazenedi-	RR′—N—C(═S)—CR″R′″—N═N—
acetothioamides),	CR″″R″″′—C(═O)—NR″″″R″″″′
Poly(diazenedi-	for diazenediacetothioamides, where R, R′,
formothioamides), and	R″, R″′, R″″, R″″′, R″″″, and R″″″′ represent
Poly(diazenedi-	H, NH₂, or any organic functional group
acetothioamides)	wherein the number of carbon atoms ranges
(N—S Tridentates	from 0 to 40, optionally having halogen or
and N—S Hexadentates)	polarizing or water-insolubilizing/
	solubilizing groups attached. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N—S Valence	R—O—C(═S)—N═N—C(═S)—O—R′,
Stabilizer #20:	R—O—C(═S)—CR′R″—N═N—
Diazenedicarbothioic acids,	CR′″R″″—C(═S)—O—R″″′,
Diazenedi-	R—O—C(═S)—N═N—C(═O)—O—R′,
carbodithioic acids,	or R—O—C(═S)—CR′R″—N═′N—
Bis(diazenedi-	CR″′R″″—C(═O)—O—R″″′ for
carbothioic acids),	diazenedicarbothioic acids, and R—S—
Bis(diazenedi-	C(═S)—N═N—C(═S)—S—R′ or
carbodithioic acids),	R—S—C(═S)—CR′R″—N═N—
Poly(diazenedi-	CR″′R″″—C(═S)—S—R″″′ for
carbothioic acids),	diazenedicarbodithoic acids, where R, R′,
Poly(diazenedi-	R″, R″′, R″″, and R″′″ represent H, NH₂,
carbodithioic acids) and	or any organic functional group wherein the
derivatives thereof	number of carbon atoms ranges from 0 to 40,
(N—S Tridentates	optionally having halogen or polarizing or
and N—S Hexadentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—S Valence	RC(═S)—N═N—C(═S)—R′ or
Stabilizer #21:	RC(═S)—N═N—C(═O)—R′ for
Diazenedi-	diazenediformothioaldehydes, and RC(═S)—
formothioaldehydes,	CR′R″—N═N—CR″′R″″—C(═S)—R′″″ or
Diazenedi-	RC(═S)—CR′R″—N═N—CR″′R″″—
acetothioaldehydes,	C(═O)—R″″′ for diazenediaceto-
Bis(diazenedi-	thioaldehydes, where R, R′, R″, R″′, R″″,
formothioaldehydes),	and R″″′ represent H, NH₂, or any organic
Bis(diazenedi-	functional group wherein the number of
acetothioaldehydes),	carbon atoms ranges from 0 to 40, optionally
Poly(diazenedi-	having halogen or polarizing or water-
formothioaldehydes), and	insolubilizing/solubilizing groups attached.
Poly(diazenedi-	Ligand can also contain nonbinding N, O, S,
acetothioaldehydes)	or P atoms.
(N—S Tridentates and
N—S Hexadentates)
N—S Valence	R—N═N—CR′═N—NR″R″′, where R,
Stabilizer #22:	R′, R″, and R″′ represent H, or any organic
Ortho-thio (or -mercapto)	functional group wherein the number of
Substituted Formazans,	carbon atoms ranges from 0 to 40, optionally
Bis(o-thio or -mercapto	having halogen or polarizing or water-
substituted formazans),	insolubilizing/solubilizing groups
and Poly(o-thio or	attached. (Must include ortho-thio or
-mercapto substituted	mercapto substituted aryl R derivatives,
formazans) (N—S	and beta-thio or mercapto substituted alkyl
Bidentates, N—S	R derivatives.) Ligand can also contain
Tridentates, N—S	nonbinding N, O, S, or P atoms.
Tetradentates, and
N—S Hexadentates)
N—S Valence	RR′C═N—NC═R″R″′ or
Stabilizer #23:	RR′C═N—NR″R″′ (for ketazines),
Ortho-thio (or -mercapto)	where R, R′, R″, and R″′ represent H, or any
Substituted Azines	organic functional group wherein the number
(including ketazines),	of carbon atoms ranges from 0 to 40,
Bis(o-thio or mercapto	optionally having halogen or polarizing or
substituted azines), and	water-insolubilizing/solubilizing groups
Poly(o-thio or mercapto	attached. (Must include ortho-thio or
substituted azines)	mercapto substituted aryl R derivatives,
(N—S Bidentates,	and beta-thio or mercapto substituted alkyl
N—S Tridentates,	R derivatives.) Ligand can also contain
N—S Tetradentates,	nonbinding N, O, S, or P atoms.
and N—S Hexadentates)
N—S Valence	RR′C═N—R″, where R, R′, and R″
Stabilizer #24:	represent H, or any organic functional group
Schiff Bases with one	wherein the number of carbon atoms ranges
Imine (C═N) Group and	from 0 to 40, optionally having halogen or
with ortho- or alpha- or	polarizing or water-insolubilizing/
beta-thio or mercapto or	solubilizing groups attached. (Must contain
thiocarbonyl substitution	ortho- or alpha- or beta- thio or mercapto
(N—S Bidentates,	or thiocarbonyl substitution.) Ligand can also
N—S Tridentates,	contain nonbinding N, O, S, or P atoms.
N—S Tetradentates,
N—S Pentadentates,
or N—S Hexadentates).
Also includes Schiff Bases
derived from the reaction of
carbonyl compounds with
dithiocarbazates, and
hydrazones with ortho-S
substitution.
N—S Valence	RR′C═N—R″—N═CR″′R″″ or
Stabilizer #25:	R—N═C—R′—C═N—R′ or
Schiff Bases with two	RC═N—R′—N═CR″, where R, R′, R″,
Imine (C═N) Groups	R″′, and R″″ represent H, or any organic
and with ortho- or alpha-	functional group wherein the number of
or beta-thio or mercapto or	carbon atoms ranges from 0 to 40, optionally
thiocarbonyl substitution	having halogen or polarizing or water-
(N—S Tridentates,	insolubilizing/solubilizing groups attached.
N—S Tetradentates,	(Must contain ortho- or alpha- or beta-thio or
N—S Pentadentates,	mercapto or thiocarbonyl substitution.)
or N—S Hexadentates).	Ligand can also contain nonbinding N, O, S,
Also includes Schiff Bases	or P atoms.
derived from the reaction of
carbonyl compounds with
dithiocarbazates, and
hydrazones with
ortho-S substitution.
N—S Valence	N(—R—N═CR′R″)₃, where R, R′, and R″
Stabilizer #26:	represent H, or any organic functional group
Schiff Bases with three	wherein the number of carbon atoms ranges
Imine (C═N) Groups and	from 0 to 40, optionally having halogen or
with ortho- or alpha- or	polarizing or water-insolubilizing/
beta- thio or mercapto or	solubilizing groups attached. (Must contain
thiocarbonyl substitution	ortho- or alpha- or beta-thio or mercapto or
(N—S Tetradentates,	thiocarbonyl substitution.) Ligand can also
N—S Pentadentates,	contain nonbinding N, O, S, or P atoms.
or N—S Hexadentates).
Also includes Schiff Bases
derived from the reaction of
carbonyl compounds with
dithiocarbazates, and
hydrazones with ortho-S
substitution.
N—S Valence	[R—CR′(—NR″R″′)]_x—R″″—[C(—
Stabilizer #27:	SR″″′)R″″″R″″″′]_y, [R—CR′(—NR″R″′)]_x—
Thioalkyl Amines	R″″—[C(—S—S—R″″′)R″″″R″″″′]_y, or
(Aminothiols or	[R—CR′(—NR″R″′)]_x—R″″—
Aminodisulfides) and	LC(═S)R″″′]_yfor thioalkyl amines; and
Thioalkyl Imines	[R—C(═NR′)]_x—R″—[C(—
(Iminothiols or	SR″′)R″″R″″′]_y, [R—C(═NR′)]_x—R″—
Iminodisulfides)	[C(—S—[C(═S)R″′]_yfor thioalkyl imines,
(N—S Bidentates,	where R, R′, H, NH₂, or any organic
N—S Tridentates,	functional group wherein the number of
N—S Tetradentates, and	carbon atoms ranges from 0 to 40, optionally
N—S Hexadentates)	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached,
	and x and y = 1-6. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N—S Valence	[R(—NR′R″)(—SR″′)],
Stabilizer #28:	[R(—NR′R″)(—S—S—R″′)],
Thioaryl Amines and	[R(—NR′R″)(—C(═S)R″′],
Thioaryl Imines (N—S	[R(—NR′R″)_x]₂S,
Bidentates, N—S	[R(—NR′R″)_x]₂₋₃R″′(—SR′″′)_y,
Tridentates, N—S	[R(—SR′)_x]₂₋₃R″(—NR″′R″″)_y,
Tetradentates, and	[R(—NR′R″)_x]₂S₂, and
N—S Hexadentates)	[R(—NR′R″)_x]₂R″′(C(═S))_yR″″
	for thioaryl amines; and
	[R(—SR′)_x]NH or [R(—SR′)_x]_{2NHNH for}
	thioaryl imines, where R, R′, R″, R″′, and
	R″″ represent H, NH₂, or any organic
	functional group wherein the number of
	carbon atoms ranges from 0 to 40, optionally
	having halogen or polanzing or water-
	insolubilizing/solubilizing groups attached,
	and x = 0-2 and y = 1-4. Ligand can also
	contain nonbinding N, O, S, or P atoms.

N—S Valence	Five membered heterocyclic ring(s)
Stabilizer #29:	containing one, two, three, or four nitrogen
Five-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	sulfur-containing substituents (usually thiols,
containing One, Two,	mercaptans, disulfides, or thiocarbonyls) that
Three, or Four Nitrogen	constitute S binding sites. Can include other
Atoms at least one	ring systems bound to the heterocyclic ring
additional Sulfur Atom	or to the S-containing substituent, but they
Binding Site not in a Ring	do not coordinate with the stabilized, high
(N—S Bidentates,	valence metal ion. Ring(s) can also contain
N—S Tridentates,	O, S, or P atoms. This 5-membered ring(s)
N—S Tetradentates,	and/or attached, uncoordinating rings and/or
or N—S Hexadentates)	S-containing substituent(s) may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—S Valence	Six membered heterocyclic ring(s)
Stabilizer #30:	containing one, two, three, or four nitrogen
Six-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	sulfur-containing substituents (usually thiols,
containing One, Two,	mercaptans, disulfides, or thiocarbonyls) that
Three, or Four Nitrogen	constitute S binding sites. Can include other
Atoms at least one	ring systems bound to the heterocyclic ring
additional Sulfur Atom	or to the S-containing substituent, but they
Binding Site not in a Ring	do not coordinate with the stabilized, high
(N—S Bidentates,	valence metal ion. Ring(s) can also contain
N—S Tridentates,	O, S, or P atoms. This 6-membered ring(s)
N—S Tetradentates,	and/or attached, uncoordinating rings and/or
or N—S Hexadentates)	S-containing substituent(s) may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—S Valence	Five membered heterocyclic ring(s)
Stabilizer #31:	containing one or two sulfur atoms. In
Five-Membered	addition, ligand contains additional nitrogen-
Heterocyclic Rings	containing substituents (usually amines,
containing One or Two	imines, or hydrazides) that constitute N
Sulfur Atoms at least one	binding sites. Can include other ring systems
additional Nitrogen Atom	bound to the heterocyclic ring or to the
Binding Site not in a Ring	N-containing substituent, but they do not
(N—S Bidentates,	coordinate with the stabilized, high valence
N—S Tridentates,	metal ion. Ring(s) can also contain O, S,
N—S Tetradentates,	or P atoms. This 5-membered ring(s) and/or
or N—S Hexadentates)	attached, uncoordinating rings and/or
	N-containingsubstituent(s) may or may
	not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—S Valence	Six membered heterocyclic ring(s)
Stabilizer #32:	containing one or two sulfur atoms. In
Six-Membered	addition, ligand contains additional nitrogen-
Heterocyclic Rings	containing substituents (usually amines,
containing One or Two	imines, or hydrazides) that constitute N
Sulfur Atoms at least one	binding sites. Can include other ring systems
additional Nitrogen Atom	bound to the heterocyclic ring or to the
Binding Site not in a Ring	N-containing substituent, but they do not
(N—S Bidentates,	coordinate with the stabilized, high valence
N—S Tridentates,	metal ion. Ring(s) can also contain O, S, or
N—S Tetradentates,	P atoms. This 6-membered ring(s) and/or
or N—S Hexadentates)	attached, uncoordinating rings and/or
	N-containingsubstituent(s) may or may
	not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—S Valence	Five membered heterocyclic ring(s)
Stabilizer #33:	containing one, two, three, or four nitrogen
Five-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	sulfur-containing rings that constitute S
containing One, Two,	binding sites. Can include other ring systems
Three, or Four Nitrogen	bound to the N- or S-containing heterocyclic
Atoms at least one	rings, but they do not coordinate with the
additional Sulfur Atom	stabilized, high valence metal ion. Ring(s)
Binding Site in a Separate	can also contain O, S, or P atoms. This
Ring (N—S Bidentates,	5-membered ring(s) and/or additional
N—S Tridentates,	S-containing ring(s) and/or attached,
N—S Tetradentates)	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—S Valence	Six membered heterocyclic ring(s)
Stabilizer #34:	containing one, two, three, or four nitrogen
Six-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	sulfur-containing rings that constitute S
containing One, Two,	binding sites. Can include other ring systems
Three, or Four Nitrogen	bound to the N- or S- containing heterocyclic
Atoms at least one	rings, but they do not coordinate with the
additional Sulfur Atom	stabilized, high valence metal ion. Ring(s)
Binding Site in a Separate	can also contain O, S, or P atoms. This
Ring (N—S Bidentates,	6-membered ring(s) and/or additional
N—S Tridentates,	S-containing ring(s) and/or attached,
N—S Tetradentates)	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—S Valence	Macrocyclic ligands containing two, three,
Stabilizer #35:	four, six, eight, or ten binding sites
Two-, Three-, Four-,	composed of nitrogen and sulfur to valence
Six-, Eight-, and Ten-	stabilize the central metal ion. Can include
Membered Macrocyclics,	other hydrocarbon or ring systems bound to
Macrobicyclics, and	this macrocyclic ligand, but they do not
Macropolycyclics	coordinate with the stabilized, high valence
(including Catapinands,	metal ion. This ligand and/or attached,
Cryptands, Cyclidenes, and	uncoordinating hydrocarbons/rings may or
Sepulchrates) wherein all	may not have halogen or polarizing or water-
Binding Sites are composed	insolubilizing/solubilizing groups attached.
of Nitrogen (usually amine
or imine groups) or Sulfur
(usually thiols, mercaptans,
or thiocarbonyls) and are
not contained in
Component Heterocyclic
Rings (N—S Bidentates,
N—S Tridentates,
N—S Tetradentates,
and N—S Hexadentates)
N—S Valence	Macrocyclic ligands containing a total of
Stabilizer #36:	four, six, eight, or ten heterocyclic rings
Four-, Six-, Eight-,	containing and nitrogen or sulfur bindingc
or Ten-Membered	sites. Can include other hydrocarbon/ring
Macrocyclics,	systems bound to this macrocyclic ligand,
Macrobicyclics,	but they do not coordinate with the
Macropolycyclics	stabilized, high valence metal ion. This
(including Catapinands,	ligand and/or attached, uncoordinating
Cryptands, Cyclidenes,	hydrocarbon/rings may or may not have
and Sepulchrates)	halogen or polarizing or water-insolubilizing
wherein all Binding Sites	groups attached.
are composed of Nitrogen
or Sulfur and are contained
in Component Heterocyclic
Rings (N—S Bidentates,
N—S Tridentates,
N—S Tetradentates,
or N—S Hexadentates)
N—S Valence	Macrocyclic ligands containing at least one
Stabilizer #37:	heterocyclic ring. These heterocyclic rings
Four-, Six-, Eight-,	provide nitrogen or sulfur binding sites to
or Ten-Membered	valence stabilize the central metal ion. Other
Macrocyclics,	amine, imine, thiol, mercapto, or
Macrobicyclics, and	thiocarbonyl binding sites can also be
Macropolycyclics	included in the macrocyclic ligand, so long
(including Catapinands,	as the total number of binding sites is four,
Cryptands, Cyclidenes,	six, eight, or ten. Can include other
and Sepulchrates)	hydrocarbon/ring systems bound to this
wherein all Binding Sites	macrocyclic ligand, but they do not
are composed of Nitrogen	coordinate with the stabilized, high valence
or Sulfur and are contained	metal ion. This ligand and/or attached,
in a Combination of	uncoordinating hydrocarbon/rings may or
Heterocyclic Rings and	may not have halogen or polarizing or water-
Amine, Imine, Thiol,	insolubilizing groups attached.
Mercapto, or Thiocarbonyl
Groups (N—S Bidentates,
N—S Tridentates,
N—S Tetradentates,
or N—S Hexadentates)
N—O Valence	R′—N(—OH)—C(—R)═N—R″, where R,
Stabilizer #1:	R′, and R″ represent H or any organic
N—Hydroxy(or N,N′-	functional group wherein the number of
dihydroxy)amidines and	carbon atoms ranges from 0 to 40, optionally
N—Hydroxy(or N,N′-	having halogen or polarizing or water-insol
dihydroxy)diamidines	ubilizing/solubilizing groups attached.
(N—O Bidentates,	Ligand can also contain nonbinding N, O, S,
N—O Tridentates,	or P atoms.
or N—O Tetradentates)
N—O Valence	RR′—N—C(═NH)—NR″—CO—NR″′R″″
Stabilizer #2:	for guanylureas, and RR′—N—C(═NH)—
Guanylureas,	NR″—NH—CO—NR″′R″″ for
Guanidinoureas,	guanidinoureas, where R, R′, R″, R″′, and
Bis(guanylureas),	R″″ represent H, NH₂, or any organic
Bis(guanidinoureas),	functional group wherein the number of
Poly(guanylureas), and	carbon atoms ranges from 0 to 40, optionally
Poly(guanidinoureas)	having halogen or polarizing or water-
(N—O Bidentates and	insolubilizing/solubilizing groups attached.
N—O Tetradentates)	Ligand can also contain nonbinding N, O, S,
	or P atoms.
N—O Valence	RR′—N—C(═NH)—NR″—CO—R″′ for
Stabilizer #3:	N-amidinoamides, or RR′—N—C(═NH)—
Amidinoamides,	CR″R″′—CO—N—R″″R″″′
Guanidinoamides,	for 2-amidinoacetamides, and
Bis(amidinoamides),	RR′—N—C(═NH)—NR″—NH—CO—R″′
Bis(guanidinoamides),	for guanidinoamides, where R, R′, R″, R″′,
Poly(amidinoamides), and	R″″, and R″″′ represent H, NH₂, or
Poly(guanidinoamides)	any organic functional group wherein the
(including both N-	number of carbon atoms ranges from 0 to 40,
amidinoamides and	optionally having halogen or polarizing or
2-amidinoacetamides)	water-insolubilizing/solubilizing groups
(N—O Bidentates	attached. Ligand can also contain nonbinding
and N—O Tetradentates)	N, O, S, or P atoms.
N—O Valence	R—C(═NH)—NR′—CO—R″, where R,
Stabilizer #4:	R′, and R″, and R′″ represent H or any
Imidoylamides,	organic functional group wherein the number
Bis(imidoylamides),	of carbon atoms ranges from 0 to 40,
Poly(imidoylamides)	optionally having halogen or polarizing or
(N—O Bidentates and	water-insolubilizing/solubilizing groups
N—O Tetradentates)	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—O Valence	RR′—N—C(═NH)—O—CO—NR″R″′,
Stabilizer #5:	where R, R′, R″, and R″′ represent H, NH₂,
O-Amidinocarbamates,	or any organic functional group wherein the
Bis(O-amidinocarbamates),	number of carbon atoms ranges from 0 to 40,
and Poly(O-	optionally having halogen or polarizing or
amidinocarbamates)	water-insolubilizing/solubilizing groups
(N—O Bidentates and	attached. Ligand can also contain nonbinding
N—O Tetradentates)	N, O, S, or P atoms.
N—O Valence	RR′—N—C(═NH)—S—CO—NR″R″′,
Stabilizer #6:	where R, R′, R″, and R″′ represent H, NH₂,
5-Amidinothiocarbamates,	or any organic functional group wherein the
Bis(S-amidinothio-	number of carbon atoms ranges from 0 to 40,
carbamates), and Poly(S-	optionally having halogen or polarizing or
amidinothiocarbamates)	water-insolubilizing/solubilizing groups
(N—O Bidentates and	attached. Ligand can also contain nonbinding
N—O Tetradentates)	N, O, S, or P atoms.
N—O Valence	(NH═)(NH═)P(OR)(OR′), where R, R′, and
Stabilizer #7:	R″ represent H, NH₂, or any organic
Diimidosulfuric Acid,	functional group wherein the number of
Bis(diimidosulfuric	carbon atoms ranges from 0 to 40, optionally
acid), and derivatives	having halogen or polarizing or water-
thereof (N—O	insolubilizing/solubilizing groups attached.
Bidentates and N—O	Ligand can also contain nonbinding N, O, S,
Tetradentates)	or P atoms.
N—O Valence	(NH═)P(—OR)(—OR′)(—OR″), where R,
Stabilizer #8:	R′, and R″ represent H, NH₂, or any organic
Phosphorimidic Acid,	functional group wherein the number of
Bis(phosphorimidic acid);	carbon atoms ranges from 0 to 40, optionally
and Poly(phosphorimidic	having halogen or polarizing or water-
acid), and derivatives	insolubilizing/solubilizing groups attached.
thereof (N—O Bidentates)	Ligand can also contain nonbinding N, O, S,
	or P atoms.
N—O Valence	(O═)P(—NRR′)(—NR″R″′)(—NR″″R″″′),
Stabilizer #9:	where R, R′, R″, R″′, R″″, and R″″′ represent H,
Phosphoric Triamides,	NH₂, or any organic functional group
Bis(phosphoric triamides),	wherein the number of carbon atoms ranges
and Poly(phosphoric	from 0 to 40, optionally having halogen or
triamides) (N—O	polarizing or water-insolubilizing/
Bidentates and	solubilizing groups attached. Ligand can also
N—O Tetradentates)	contain nonbinding N, O, S, or P atoms.
N—O Valence	(O═)P(—NRR′)(—OR″)(—OR″′)
Stabilizer #10:	for phosphoramidic acid and (O═)P(—
Phosphoramidic Acid,	NRR′)(—NR″R″′)(—OR″″) for
Phosphorodiamidic Acid,	phosphorodiamidic acid, where R, R′, R″,
Bis(phosphoramidic acid),	R″′, and R″″represent H, NH₂, or any
Bis(phosphorodiamidic	organic functional group wherein the number
acid), Poly(phosphor-	of carbon atoms ranges from 0 to 40,
amidic acid), Poly(phosp-	optionally having halogen or polarizing or
horodiamidic acid), and	water-insolubilizing/solubilizing groups
derivatives thereof	attached. Ligand can also contain nonbinding
(N—O Bidentates	N, O, S, or P atoms.
and N—O Tetradentates)
N—O Valence	R′—C(═O)—N═C(—R)(—NHR″), where
Stabilizer #11:	R is an aromatic derivative (i.e. —C₆H₅),
N-Acyl 7-Aminobenzyl-	and R′and R″ represent H, NH₂, or any
idenimines (N—O	organic functional group wherein the number
Bidentates or	of carbon atoms ranges from 0 to 40,
N—O Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—O Valence	R—C(═NOH)—R′ for oximes, and
Stabilizer #12:	R—C(═NOH)—C(═NOH)—R′ for
Oximes, Dioximes,	dioximes, where R and R′ represent H, NH₂,
and Poly(oximes)	or any organic functional group wherein the
(N—O Bidentates,	number of carbon atoms ranges from 0 to 40,
N—O Tridentates,	optionally having halogen or polarizing or
and N—O Tetradentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—O Valence	R—C(═O)—C(═NOH)—R′, where R and
Stabilizer #13:	R′ represent H, NH₂, or any organic
Carbonyl oximes,	functional group wherein the number of
Bis(carbonyl oximes),	carbon atoms ranges from 0 to 40, optionally
and Poly(carbonyl oximes)	having halogen or polarizing or water-
(N—O Bidentates,	insolubilizing/solubilizing groups attached.
N—O Tridentates,	Ligand can also contain nonbinding N, O, S,
and N—O Tetradentates)	or P atoms.
N—O Valence	R—C(═N—R″)—C(═NOH)—R′, where
Stabilizer #14:	R, R′, and R″ represent H, NH₂, or any
Imine oximes,	organic functional group wherein the
Bis(imine oximes), and	number of carbon atoms ranges from 0 to 40,
Poly(imine oximes)	optionally having halogen or polarizing or
(including 2-nitrogen	water-insolubilizing/solubilizing groups
heterocyclic oximes)	attached. Ligand can also contain nonbinding
(N—O Bidentates,	N, O, S, or P atoms.
N—O Tridentates,
N—O Tetradentates,
and N—O Hexadentates)
N—O Valence	R—CH(—OH)—C(═NOH)—R′, where R,
Stabilizer #15:	R′, and R″ represent H, NH₂, or any
Hydroxy oximes,	organic functional group wherein the number
Bis(hydroxy oximes), and	of carbon atoms ranges from 0 to 40,
Poly(hydroxy oximes)	optionally having halogen or polarizing or
(including 2-oxygen	water-insolubilizing/solubilizing groups
heterocyclic oximes)	attached. Ligand can also contain nonbinding
(N—O Bidentates,	N, O, S, or P atoms.
N—O Tridentates,
N—O Tetradentates,
and N—O Hexadentates)
N—O Valence	RR′—C(—NH—R″)—C(═NOH)—R′″
Stabilizer #16:	where R, R′, R″, and R″′represent H, NH₂,
Amino oximes,	or any organic functional group wherein the
Bis(amino oximes), and	number of carbon atoms ranges from 0 to 40,
Poly(amino oximes)	optionally having halogen or polarizing or
(N—O Bidentates,	water-insolubilizing/solubilizing groups
N—O Tridentates,	attached. Ligand can also contain nonbinding
N—O Tetradentates,	N, O, S, or P atoms.
and N—O Hexadentates)
N—O Valence	RR′—N—C(═NOH)—R″, where R, R′,
Stabilizer #17:	and R″ represent H, NH₂, or any organic
Amido oximes,	functional group wherein the number of
Bis(amido oximes), and	carbon atoms ranges from 0 to 40, optionally
Poly(amido oximes)	having halogen or polarizing or water-
(N—O Bidentates,	insolubilizing/solubilizing groups attached.
N—O Tridentates,	Ligand can also contain nonbinding N, O, S,
N—O Tetradentates,	or P atoms.
and N—O Hexadentates)
N—O Valence	R—N═N—C(═NOH)—R′ or RR′C—
Stabilizer #18:	═N—NR″—C(═NOH)—R″′, where R,
Azo oximes,	R′, R″, and R″′represent H, NH₂, or any
Bis(azo oximes),	organic functional group wherein the
and Poly(azo oximes)	number of carbon atoms ranges from 0 to 40,
(N—O Bidentates,	optionally having halogen or polarizing or
N—O Tridentates,	water-insolubilizing/solubilizing groups
N—O Tetradentates,	attached. (R is typically an aryl group.)
and N—O Hexadentates).	Ligand can also contain nonbinding N, O, S,
Also includes	or P atoms.
hydrazone oximes.
N—O Valence	o-(ON—)(HO-)Ar, where Ar represents an
Stabilizer #19:	aromatic group or heterocyclic wherein the
2—Nitrosophenols	number of carbon atoms ranges from 6 to 40,
(o-Quinone monoximes)	optionally having halogen or polarizing or
(N—O Bidentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—O Valence	o-(O₂N—)(HO-)Ar, where Ar represents an
Stabilizer #20:	aromatic group or heterocyclic wherein the
2—Nitrophenols	number of carbon atoms ranges from 6 to 40,
(N—O Bidentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms.
N—O Valence	R—C(═O)—NR′—OH or
Stabilizer #21:	R—C(—OH)═N—OH, where R and R′
Hydroxamates	represent H, NH₂, or any organic functional
(Hydroxylamines),	group wherein the number of carbon atoms
Bis(hydroxamates), and	ranges from 0 to 40, optionally having
Poly(hydroxamates)	halogen or polarizing or water-
(N—O Bidentates,	insolubilizing/solubilizing groups
N—O Tetradentates,	attached. Ligand can also contain nonbinding
and N—O Hexadentates)	N, O, S, or P atoms.
N—O Valence	R—N(—NO)—OH, where R represents
Stabilizer #22:	any organic functional group wherein the
N-Nitrosohydroxylamines,	number of carbon atoms ranges from 1 to 40,
Bis(N-nitrosohydroxyl-	optionally having halogen or polarizing or
amines), and Poly(N-	water insolubilizing/solubilizing groups
nitrosohydroxylamines)	attached. (R is typically an aryl or
(N—O Bidentates,	heterocyclic group.) Ligand can also contain
N—O Tetradentates,	nonbinding N, O, S. or P atoms.
and N—O Hexadentates)
N—O Valence	R—CH(—NHR′)—C(═O)(—OH) for
Stabilizer #23:	amino acids and ortho-aminocarboxylic
Amino Acids and	acids, and R—CH(—NHR′)—C(═O)—
ortho-Aminocarboxylic	(NR″—)CH(—R″′)—C(═O)(—OH)
Acids, Peptides,	for peptides, where R, R′, R″, and R″′
Polypeptides, and Proteins	represent any organic functional group
[N—O Bidentates,	wherein the number of carbon atoms ranges
N—O Tridentates, and	from 1 to 40, optionally having halogen or
N—O Tetradentates;	polarizing or water-insolubilizing/
possibly S—O dentates	solubilizing groups attached. Ligand can also
for sulfur-contg. examples	contain nonbinding N, O, S, or P atoms.
such as penicillamine and
cystine]
N—O Valence	RCONR′R″, where R, R′, and R″ represent
Stabilizer #24:	H, NH₂, or any organic functional group
Amides, Bis(amides),	wherein N—O the number of carbon atoms
and Poly(amides),	ranges from 0 to 40, optionally having
including lactams	halogen or polarizing or water-
(N—O Bidentates,	insolubilizing/solubilizing groups
Tridentates, and	attached. Ligand can also contain nonbinding
N—O Tetradentates)	N, O, S, or P atoms.
N—O Valence	RR′—N—C(═O)—NR″—N═CR″′R″″,
Stabilizer #25:	where R, R′, R″, R″′, and R″″ represent H,
Semicarbazones,	or any organic functional group wherein the
Bis(semicarbazones), and	number of carbon atoms ranges from 0 to 40,
Poly(semicarbazones)	optionally having halogen or polarizing or
(N—O Bidentates,	water-insolubilizing/solubilizing groups
N—O Tetradentates, and	attached. Ligand can also contain nonbinding
N—O Hexadentates)	N, O, S, or P atoms.
N—O Valence	R—C(═O)—NR′—N═CR″R″′, where
Stabilizer #26:	R, R′, R″, and R″′ represent H, or any
Acyl hydrazones,	organic functional group wherein the number
Bis(acyl hydrazones), and	of carbon atoms ranges from 0 to 40,
Poly(acyl hydrazones)	optionally having halogen or polarizing or
(N—O Bidentates,	water-insolubilizing/solubilizing groups
N—O Tetradentates,	attached. Ligand can also contain nonbinding
and N—O Hexadentates)	N, O, S, or P atoms.
N—O Valence	R—N═N—C(═O)—NR′—N—R″R″′,
Stabilizer #27:	where R, R′, R″, and R″′ represent H, or any
Carbazones	organic functional group wherein the number
(Diazenecarboxylic	of carbon atoms ranges from 0 to 40,
hydrazides),	optionally having halogen or polarizing or
Bis(carbazones), and	water-insolubilizing/solubilizing groups
Poly(carbazones)	attached. Ligand can also contain nonbinding
(N—O Bidentates,	N, O, S, or P atoms.
N—O Tetradentates,
and N—O Hexadentates)
N—O Valence	R—N═N—R′ for azo compounds,
Stabilizer #28:	R—N═N—NH—R′ for triazenes, where R,
Azo compounds including	and R′ represent H or any organic functional
triazenes with hydroxyl	group wherein the number of carbon atoms
or carboxy or carbonyl	ranges from 0 to 40, optionally having
substitution at the ortho-	halogen or polarizing or water-
(for aryl) or alpha- or beta-	insolubilizing/solubilizing groups
(for alkyl) positions,	attached. (Must include ortho-hydroxy or
Bis[o-(HO—) or alpha-	carboxy or carbonyl substituted aryl azo
or beta-(HO—)azo	compounds, and alpha- or beta-hydroxy or
compounds], or	carboxy or carbonyl alkyl azo compounds.)
Poly[o-(HO—) or alpha-	Ligand can also contain nonbinding N, O, S,
or beta-(HO—)azo	or P atoms.
compounds) (N—O
Bidentates, N—O
Tridentates, N—O
Tetradentates, or
N—O Hexadentates)
N—O Valence	R—N═N—C(═O)—NR′R″
Stabilizer #29:	for diazeneformamides, and
Diazeneformamides,	R—N═N—CR′R″—C(═O)—NR′″R ″″
Diazeneacetamides,	for diazeneacetamides, where R, R′, R″, R″′,
Bis(diazeneformamides),	and R″″ represent H, NH₂, or any organic
Bis(diazeneacetamides),	functional group wherein the number of
Poly(diazeneformamides),	carbon atoms ranges from 0 to 40, optionally
and Poly(diazene-	having halogen or polarizing or water-
acetamides)	insolubilizing/solubilizing groups attached.
(N—O Bidentates,	Ligand can also contain nonbinding N, O, S,
N—O Tetradentates,	or P atoms.
and N—O Hexadentates)
N—O Valence	R—N═N—C(═O)—O—R′
Stabilizer #30:	for diazeneformic acid, and
Diazeneformic acids,	R—N═N—CR′R″—C(═O)—O—R″′
Diazeneacetic acids,	for diazeneacetic acid, where R, R′, R″, and
Bis(diazeneformic acids),	R″′ represent H, NH₂, or any organic
Bis(diazeneacetic acids),	functional group wherein the number of
Poly(diazeneformic acids),	carbon atoms ranges from 0 to 40, optionally
Poly(diazeneacetic acids),	having halogen or polarizing or water-
and derivatives thereof	insolubilizing/solubilizing groups attached.
(N—O Bidentates,	Ligand can also contain nonbinding N, O, S,
N—O Tetradentates,	or P atoms.
N—O Hexadentates)
N—O Valence	R—N═N—C(═O)—R′
Stabilizer #31:	for diazeneformaldehydes, and
Diazeneformaldehydes,	R—N═N—CR′R″—C(═O)—R″′ for
Diazeneacetaldehydes,	diazeneacetaldehydes, where R, R′, R″, and
Bis(diazene-	R″′ represent H, NH₂, or any organic
formaldehydes),	functional group wherein the number of
Bis(diazene-	carbon atoms ranges from 0 to 40, optionally
acetaldehydes),	having halogen or polarizing or water-
Poly(diazene-	insolubilizing/solubilizing groups attached.
formaldehydes), and	Ligand can also contain nonbinding N, O, S,
Poly(diazene-	or P atoms.
acetaldehydes)
(N—O Bidentates,
N—O Tetradentates
and N—O Hexadentates)
N—O Valence	RR′—N—C(═O)—NN—C(═O)—NR″R″′
Stabilizer #32:	for diazenediformamides, and RR′—N—
Diazenediformamides,	C(═O)—CR″R″′—N═N—CR″″R″″′—
Diazenediacetamides,	C(═O)—NR″″″R″″″′for diazenedi-
Bis(diazenedi-	acetamides, where R, R′, R″, R″′, R″″, R″″′,
formamides),	R″″″, and R″″″′ represent H, NH₂, or any
Bis(diazene-	organic functional group wherein the
diacetamides),	number of carbon atoms ranges from
Poly(diazenedi-	0 to 40, optionally having halogen or
formamides), and	polarizing or water-insolubilizing/
Poly(diazenedi-	solubilizing groups attached. Ligand can also
acetamides)	contain nonbinding N, O, S, or P atoms.
(N—O Tridentates
and N—O Hexadentates)
N—O Valence	R—O—C(═O)—N═N—C(═O)—O—R′
Stabilizer #33:	for diazenediforrnic acid, and
Diazenediformic acids,	R—O—C(═O)—CR′R″N═N—CR″′R″″—
Diazenediacetic acids,	C(═O)—R′″″ for diazenediacetic acid,
Bis(diazenediformic acids),	where R, R′, R″, R″′, R″″, and R″″′ represent
Bis(diazenediacetic acids),	H, NH₂, or any organic functional group
Poly(diazenediformic	wherein the number of carbon atoms ranges
acids), Poly(diazene-	from 0 to 40, optionally having halogen or
diacetic acids) and	polarizing or water-insolubilizing/
derivatives thereof	solubilizing groups attached.
(N—O Tridentates	Ligand can also contain nonbinding
and N—O Hexadentates)	N, O, S, or P atoms.
N—O Valence	RC(═O)—N═N—C(═O)—R′
Stabilizer #34:	for diazenediformaldehydes, and
Diazenediformaldehydes,	RC(═O)—CR ′R″—N═N—CR″′R″″—
Diazenediacetaldehydes,	C(═O)—R″″′ for diazenediacetaldehydes,
Bis(diazenedi-	where R, R′, R″, R″′, R″″, and R″″′ represent
formaldehydes),	H, NH₂, or any organic functional group
Bis(diazenedi-	wherein the number of carbon atoms ranges
acetaldehydes),	from 0 to 40, optionally having halogen or
Poly(diazenedi-	polarizing or water-insolubilizing/
formaldehydes), and	solubilizing groups attached. Ligand can
Poly(diazenedi-	also contain nonbinding N, O, S, or
acetaldehydes)	P atoms.
(N—O Tridentates
and N—O Hexadentates)
N—O Valence	R—N═N—CR′═N—NR″R″′, where
Stabilizer #35:	R, R′, R″, and R″′ represent H, or any
Ortho-hydroxy (or	organic functional group wherein the number
-carboxy) Substituted	of carbon atoms ranges from 0 to 40,
Formazans, Bis(o-hydroxy	optionally having halogen or polarizing or
or -carboxy substituted	water-insolubilizing/solubilizing groups
formazans), and	attached. (Must include ortho-hydroxy or
Poly(o-hydroxy or -carboxy	carboxy substituted aryl R derivatives, and
substituted formazans)	beta-hydroxy or carboxy substituted alkyl R
(N—O Bidentates,	derivatives.) Ligand can also contain
N—O Tridentates,	nonbinding N, O, S, or P atoms.
N—O Tetradentates,
and N—O Hexadentates)
N—O Valence	RR′C═N—N═CR″R″′or
Stabilizer #36:	RR′C═N—NR″R″′(for ketazines), where
Ortho-hydroxy (or	R, R′, R″, and R″′ represent H, or any
-carboxy) Substituted	organic functional group wherein the number
Azines (including	of carbon atoms ranges from 0 to 40,
ketazines), Bis(o-	optionally having halogen or polarizing or
hydroxy or carboxy	water-insolubilizing/solubilizing groups
substituted azines), and	attached. (Must include ortho-hydroxy or
Poly(o-hydroxy or	carboxy substituted aryl R derivatives,
carboxy substituted azines)	and beta- hydroxy or carboxy substituted
(N —O Bidentates,	alkyl R derivatives.) Ligand can also contain
N—O Tridentates,	nonbinding N, O, S, or P atoms.
N—O Tetradentates,
and N—O Hexadentates)
N—O Valence	RR′C═N—R″, where R, R′, and R″
Stabilizer #37:	represent H, or any organic functional group
Schiff Bases with	wherein the number of carbon atoms ranges
one Imine (C═N) Group	from 0 to 40, optionally having halogen or
and with ortho- or alpha-	polarizing or water-insolubilizing/
or beta-hydroxy or carboxy	solubilizing groups attached. (Must contain
or carbonyl substitution	ortho- or alpha- or beta- hydroxy or carboxy
(N—O Bidentates,	or carbonyl substitution.) Ligand can also
N—O Tridentates,	contain nonbinding N, O, S, or P atoms.
N—O Tetradentates,
N—O Pentadentates, or
N—O Hexadentates).
Also includes hydrazones
with ortho-O substitution.
N—O Valence	RR′C═N—R″—N═CR″′R″″ or
Stabilizer #38:	R—N═C—R′—C═N—R′ or
Schiff Bases with	RC═N—R′—N═CR″, where R, R′, R″,
two Imine (C═N) Groups	R″′, and R″″ represent H, or any organic
and with ortho- or alpha-	functional group wherein the number of
or beta-hydroxy or carboxy	carbon atoms ranges from 0 to 40, optionally
or carbonyl substitution	having halogenor polarizing or water-
(N—O Tridentates,	insolubilizing/solubilizing groups attached.
N—O Tetradentates,	(Must contain ortho- or alpha- or beta-
N—O Pentadentates, or	hydroxy or carboxy or carbonyl substitution.)
N—O Hexadentates).	Ligand can also contain nonbinding N, O, S,
Also includes hydrazones	or P atoms.
with ortho-O substitution.
N—O Valence	N(—R—N═CR′R″)₃, where R, R′, and R″
Stabilizer #39:	represent H, or any organic functional group
Schiff Bases with	wherein the number of carbon atoms ranges
three Imine (C═N)	from 0 to 40, optionally having halogen or
Groups and with ortho-	polarizing or water-insolubilizing/
or alpha- or beta-	solubilizing groups attached. (Must contain
hydroxy or carboxy or	ortho- or alpha- or beta-hydroxy or carboxy
carbonyl substitution	or carbonyl substitution.) Ligand can also
(N—O Tetradentates,	contain nonbinding N, O, S, or P atoms.
N—O Pentadentates, or
N—O Hexadentates).
Also includes hydrazones
with ortho-O substitution.
N—O Valence	[R—C(NR′R″)]_x—R″—[Si(—OR″′)_zR″″_3−z]_y
Stabilizer #40:	where R, R′, R″, R″′, and R″″ represent H,
Silylaminoalcohols	NH₂, or any organic functional group
(N—O Bidentates,	wherein the number of carbon atoms ranges
N—O Tridentates,	from 0 to 40, optionally having halogen or
N—O Tetradentates,	polarizing or water-insolubilizing/
and N—O Hexadentates)	solubilizing groups attached, and x and
	y = 1-6, z =1-3. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—O Valence	[R—C(═NR′)]_x—R″—[C(—OR″′)R″″R″″′]_y
Stabilizer #41:	or [R—C(═NR′)]_x—R″—[C(═O)R″′]_y,
Hydroxyalkyl Imines	where R, R′, R″, R″′, R″″, and R″″′ represent
(Imino Alcohols)	H, NH₂, or any organic functional group
(N—O Bidentates,	wherein the number of carbon atoms ranges
N—O Tridentates,	from 0 to 40, optionally having halogen
N—O Tetradentates,	or polarizing or water-insolubilizing/
and N—O Hexadentates)	solubilizing groups attached, and x and y =
	1-6. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—O Valence	[R(—NR′R″)(—OR″′)],
Stabilizer #42:	[R(—NR′R″)(—C(═O)R″′],
Hydroxyaryl Amines	[R(—NR′R″)_x]₂O,
and Hydroxyaryl Imines	[R(—NR′R″)_x]₂₋₃R″′(—OR′″′)_y,
(N—O Bidentates,	[R(—OR′)_x]₂₋₃R″(—NR″′R″″)_y, and
N—O Tridentates,	[R(—NR′R″)_x]₂R″″(C(═O))_yR″″ for
N—O Tetradentates,	hydroxyaryl amines; and [R(—OR′)_x]₂NH or
and N—O Hexadentates)	[R(—OR′)_x]₂NHNH for hydroxyaryl imines,
	where R, R′, R″, R″′, and R″″ represent H,
	NH₂, or any organic functional group
	wherein the number of carbon atoms ranges
	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/
	solubilizing groups attached, and
	x = O-2 and y = 1-4. Ligand can also
	contain nonbinding N, O, S, or P atoms.
N—O Valence	Five membered heterocyclic ring(s)
Stabilizer #43:	containing one, two, three, or four nitrogen
Five-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	oxygen-containing substituents (usually
containing One, Two,	hydroxy, carboxy or carbonyl groups) that
Three, or Four Nitrogen	constitute O binding sites. Can include other
Atoms at least one	ring systems bound to the heterocyclic ring
additional Oxygen Atom	or to the O-containing substituent, but they
Binding Site not in a Ring	do not coordinate with the stabilized, high
(N—O Bidentates,	valence metal ion. Ring(s) can also contain
N—O Tridentates,	O, S, or P atoms. This 5-membered ring(s)
N—O Tetradentates,	and/or attached, uncoordinating rings and/or
or N—O Hexadentates)	O-containing substituent(s) may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—O Valence	Six membered heterocyclic ring(s)
Stabilizer #44:	containing one, two, three, or four nitrogen
Six-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	oxygen-containing substituents (usually
containing One, Two,	hydroxy, carboxy, or carbonyl groups) that
Three, or Four Nitrogen	constitute O binding sites. Can include other
Atoms at least one	ring systems bound to the heterocyclic ring
additional Oxygen Atom	or to the O-containing substituent, but they
Binding Site not in a Ring	do not coordinate with the stabilized, high
(N—O Bidentates,	valence metal ion. Ring(s) can also contain
N—O Tridentates,	O, S, or P atoms. This 6-membered ring(s)
N—O Tetradentates,	and/or attached, uncoordinating rings and/or
or N—O Hexadentates)	O-containing substituent(s) may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—O Valence	Five membered heterocyclic ring(s)
Stabilizer #45:	containing one or two oxygen atoms. In
Five-Membered	addition, ligand contains additional nitrogen-
Heterocyclic Rings	containing substituents (usually amines,
containing One or	imines, or hydrazides) that constitute N
Two Oxygen Atoms at	binding sites. Can include other ring systems
least one additional	bound to the heterocyclic ring or to the
Nitrogen Atom Binding	N-containing substituent, but they do not
Site not in a Ring	coordinate with the stabilized, high valence
(N—O Bidentates,	metal ion. Ring(s) can also contain O, S,
N—O Tridentates,	or P atoms. This 5-membered ring(s) and/or
N—O Tetradentates,	attached, uncoordinating rings and/or
or N—O Hexadentates)	N-containing substituent(s) may or may
	not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—O Valence	Six membered heterocyclic ring(s)
Stabilizer #46:	containing one or two oxygen atoms. In
Six-Membered	addition, ligand contains additional nitrogen-
Heterocyclic Rings	containing substituents (usually amines,
containing One or	imines, or hydrazides) that constitute N
Two Oxygen Atoms at	binding sites. Can include other ring systems
least one additional	bound to the heterocyclic ring or to the
Nitrogen Atom Binding	N-containing substituent, but they do not
Site not in a Ring	coordinate with the stabilized, high valence
(N—O Bidentates,	metal ion. Ring(s) can also contain O, S, or
N—O Tridentates,	P atoms. This 6-membered ring(s) and/or
N—O Tetradentates,	attached, uncoordinating rings and/or
or N—O Hexadentates)	N-containingsubstituent(s) may or may
	not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—O Valence	Five membered heterocyclic ring(s)
Stabilizer #47:	containing one, two, three, or four nitrogen
Five-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	oxygen-containing rings that constitute O
containing One, Two,	binding sites. Can include other ring systems
Three, or Four	bound to the N- or O-containing heterocyclic
Nitrogen Atoms at	rings, but they do not coordinate with the
least one additional	stabilized, high valence metal ion. Ring(s)
Oxygen Atom Binding	can also contain O, S, or P atoms. This
Site in a Separate Ring	5-membered ring(s) and/or additional O—
(N—O Bidentates,	containing ring(s) and/or attached,
N—O Tridentates,	uncoordinating rings may or may not have
N—O Tetradentates)	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—O Valence	Six membered heterocyclic ring(s)
Stabilizer #48:	containing one, two, three, or four nitrogen
Six-Membered	atoms. In addition, ligand contains additional
Heterocyclic Rings	oxygen-containing rings that constitute O
containing One,	binding sites. Can include other ring systems
Two, Three, or Four	bound to the N- or O- containing heterocyclic
Nitrogen Atoms at	rings, but they do not coordinate with the
least one additional	stabilized, high valence metal ion. Ring(s)
Oxygen Atom Binding	can also contain O, S, or P atoms. This
Site in a Separate Ring	6-membered ring(s) and/or additional
(N—O Bidentates,	O-containing ring(s) and/or attached,
N—O Tridentates,	uncoordinating rings may or may not have
N—O Tetradentates)	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—O Valence	Macrocyclic ligands containing two, three,
Stabilizer #49:	four, six, eight, or ten binding sites
Two-, Three-, Four-,	composed of nitrogen and oxygen to valence
Six-, Eight-, and Ten-	stabilize the central metal ion. Can include
Membered Macrocyclics,	other hydrocarbon or ring systems bound to
Macrobicyclics,	this macrocyclic ligand, but they do not
and Macropolycyclics	coordinate with the stabilized, high valence
(including Catapinands,	metal ion. This ligand and/or attached,
Cryptands, Cyclidenes, and	uncoordinating hydrocarbons/rings may or
Sepulchrates) wherein all	may not have halogen or polarizing or water-
Binding Sites are	insolubilizing/solubilizing groups attached.
composed of Nitrogen
(usually amine or
imine groups) or Oxygen
(usually hydroxy, carboxy,
or carbonyl groupss) and
are not contained in
Component Heterocyclic
Rings (N—O Bidentates,
N—O Tridentates,
N—O Tetradentates,
and N—O Hexadentates)
N—O Valence	Macrocyclic ligands containing a total of
Stabilizer #50:	four, six, eight, or ten heterocyclic rings
Four-, Six-, Eight-,	containing nitrogen or oxygen binding sites.
or Ten-Membered	Can include other hydrocarbon/ring systems
Macrocyclics,	bound to this macrocyclic ligand, but they
Macrobicyclics, and	do not coordinate with the stabilized, high
Macropolycyclics	valence metal ion. This ligand and/or
(including Catapinands,	attached, uncoordinating hydrocarbon/rings
Cryptands, Cyclidenes,	may or may not have halogen or polarizing
and Sepulchrates)	or water-insolubilizing groups attached.
wherein all Binding
Sites are composed of
Nitrogen or Oxygen
and are contained in
Component Heterocyclic
Rings (N—O Bidentates,
N—O Tridentates, N—O
Tetradentates, or N—O
Hexadentates)
N—O Valence	Macrocyclic ligands containing at least one
Stabilizer #51:	heterocyclic ring. These heterocyclic rings
Four-, Six-, Eight-,	provide nitrogen or oxygen binding sites to
or Ten-Membered	valence stabilize the central metal ion. Other
Macrocyclics,	amine, imine, hydroxy, carboxy, or carbonyl
Macrobicyclics, and	binding sites can also be included in the
Macropolycyclics	macrocyclic ligand, so long as the total
(including Catapinands,	number of binding sites is four, six, eight,
Cryptands, Cyclidenes,	or ten. Can include other hydrocarbon/ring
and Sepulchrates)	systems bound to this macrocyclic ligand,
wherein all Binding	but they do not coordinate with the
Sites are composed of	stabilized, high valence metal ion.
Nitrogen or Oxygen and	This ligand and/or attached,
are contained in a	uncoordinating hydrocarbon/rings may or
Combination of	may not have halogen or polarizing or
Heterocyclic Rings and	water-insolubilizing groups attached.
Amine, Imine, Hydroxy,
Carboxy, or Carbonyl
Groups (N—O Bidentates,
N—O Tridentates,
N—O Tetradentates,
or N—O Hexadentates)
S—O Valence	R—C(═S)—CR′R″—C(═O)—R″′ where
Stabilizer #1:	R, R′, R″, and R″′ represent H, NH₂, or any
1,3-Monothioketones	organic functional group wherein the number
(Monothio-beta-	of carbon atoms ranges from 0 to 40,
ketonates),	optionally having halogen or polarizing or
1,3,5-Monothioketones,	water-insolubilizing/solubilizing groups
1,3,5-Dithioketones,	attached. Ligand can also contain nonbinding
Bis(1,3-Monothioketones),	N, O, S, or P atoms.
and Poly(1,3-
Monothioketones) (S—O
Bidentates, S—O
Tridentates, S—O
Tetradentates)
S—O Valence	R—C(═S)—CR′E″—C(═O)—R″′ where
Stabilizer #2:	R, R′, R″, R″′, R″″, and R″″′ represent H,
Thiomalonamides	NH₂, or any organic functional group
(Thiomalonodiamides),	wherein the number of carbon atoms ranges
Bis(thiomalonamides), and	from 0 to 40, optionally having halogen or
Polythiomalonamides	polarizing or water-insolubilizing/
(S—O Bidentates,	solubilizing groups attached. Ligand can also
S—O Tridentates,	contain nonbinding N, O, S, or P atoms.
S—O Tetradentates)
S—O Valence	RR′—N—C(═O)—CR″R″′—C(═S)—R″″
Stabilizer #3:	for 2-thioacylacetamides, and
2-Thioacylacetamides, 2-	RR′—N—C(═S)—CR″R″′—C(═O)—R″″
Acylthioacetamides,	for 2-acylthioacetamides, where R, R′, R″,
Bis(2-thioacyl-	R″′, and R″″ represent H, NH₂, or any
acetamides),	organic functional group wherein the number
Bis(2acylthio-	of carbon atoms ranges from 0 to 40,
acetamides), Poly(2-	optionally having halogen or polarizing or
thioacylacetamides), and	water-insolubilizing/solubilizing groups
Poly(2-Acylthio-	attached. Ligand can also contain
acetamides)	nonbinding N, O, S, or P atoms.
(S—O Bidentates,
S—O Tridentates,
S—O Tetradentates)
S—O Valence	RR′—N—C(═S)—S—C(═O)—N—R″R″′
Stabilizer #4:	where R, R′, R″, and R″′ represent H, NH₂or
Dithiodicarbonic	any organic functional group wherein the
Diamides,	number of carbon atoms ranges from 0 to 40,
Bis(dithiodicarbonic	optionally having halogen or polarizing or
diamides), and	water-insolubilizing/solubilizing groups
Poly(dithiodicarbonic	attached. Ligand can also contain nonbinding
diamides) (S—O	N, O, S, or P atoms.
Bidentates, S—O
Tridentates, S—O
Tetradentates)
S—O Valence	(R—O—)(R′—O—)P(═S)—
Stabilizer #5:	P(═O)(—O—R′)(—O—R′″);
Monothiohypophos-	(R—O—)(R′—S—)P(═S)—
phoric Acids,	P(═O)(—S—R″)(—O—R″′); or
Bis(monothiohypo-	(R—S—)(R′—S—)P(═S)—
phosphoric acids), and	P(═O)(—S—R″)(—S—R″′),
Poly(monothiohypo-	where R, R′, R″, and R″′ represent H, NH₂or
phosphoric acids), and	any organic functional group wherein the
derivatives thereof	number of carbon atoms ranges from 0 to 40,
(S—O Bidentates,	optionally having halogen or polarizing or
S—O Tridentates,	water-insolubilizing/solubilizing groups
S—O Tetradentates)	attached. Ligand can also contain nonbinding
	N, O, S, or P atoms. Note: these ligands are
	not to be confused with hypophosphorous
	acid derivatives (hypophosphites) (R—
	O—)R″R″′P(═O) which are very reducing
	and therefore unacceptable for stabilization
	of high valence states in metal ions.
S—O Valence	(RR′—N—)(R″R′″—N—)P(═S)(—N—
Stabilizer #6:	R″″R″″′)(—N—R″″″R″″″′), where R, R′,
Monothiohypo-	R″, R″′, R″″, R″″′, R″″″, and R″″″′ represent
phosphoramides,	H, NH₂or any organic functional group
Bis(monothiohypo-	wherein the number of carbon atoms ranges
phosphoramides), and	from 0 to 40, optionally having halogen or
Poly(monothiohypo-	polarizing or water-insolubilizing/
phosphoramides) (S—O	solubilizing groups attached. Ligand can also
Bidentates, S—O	contain nonbinding N, O, S, or P atoms.
Tridentates, S—O	Note: these ligands are not to be confused
Tetradentates)	with hypophosphorous acid derivatives
	(hypophosphites) (R—O—) R″R″′P(═O)
	which are very reducing and therefore
	unacceptable for stabilization of high
	valence states in metal ions.
S—O Valence	(R—O—)(R′—O—)P(═S)—NH—
Stabilizer #7:	P(═O)(—O—R″)(—O—R″′);
Monothioimido-	(R—O—)(R′—S—)P(S)—NH—
diphosphoric Acids,	P(═O)(—S—R″)(—0—R″′); or
Monothiohydrazido-	(R—S—)(R ′—S—)P(═S)—NH—
diphosphoric Acids,	P(═O)(—S—R″)(—S—R″′)
Bis(monothioimido-	for monothioimidodiphosphoric acids,
diphosphoric Acids),	and —NH—NH— derivatives for
Bis(monothiohydrazido-	monothiohydrazidodiphosphoric acids, where
diphosphoric Acids),	R,R′,R″, and R″′ represent H, NH₂or any
Poly(monothioimidodi-	organic functional group wherein the number
phosphoric Acid),	of carbon atoms ranges from 0 to 40,
Poly(monothiohydrazido-	optionally having halogen or polarizing or
diphosphoric Acids),	water-insolubilizing/solubilizing groups
and derivatives thereof	attached. Ligand can also contain nonbinding
(5—O Bidentates,	N, O, S, or P atoms.
S—O Tridentates,
S—O Tetradentates)
S—O Valence	(RR′—N—)(R″R″′—N—)P(═S)—NH—
Stabilizer #8:	P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′)
Monothioimidodi-	for monothiolmidodiphosphoramides, and
phosphoramides,	—NH—NH— derivatives for
Monothiohydrazidodi-	monothiohydrazidodiphosphoramides, where
phosphoramides,	R, R′, R″, R″′, R″″, R″″′, R″″″, and R′″″″
Bis(monothioimidodi-	represent H, NH₂or any organic functional
phosphoramides),	group wherein the number of carbon atoms
Bis(monothiohydrazido-	ranges from 0 to 40, optionally having
diphosphoramides),	halogen or polarizing or water-
Poly(monothioimidodi-	insolubilizing/solubilizing groups attached.
phosphoramides), and	Ligand can also contain nonbinding N, O, S,
Poly(monothiohydrazido-	or P atoms.
diphosphoramides)
(5—O Bidentates,
5—O Tridentates,
5—O Tetradentates)
S—O Valence	(RR′—N—)(R″R″′—N—)P(═S)—S—
Stabilizer #9:	P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′),
Monothiodi-	or (RR ′—N—)(R″R″′—N—)P(═S)—O—
phosphoramides,	P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′),
Bis(monothioiphos-	where R, R′, R″, R″′, R″″, R″″′, R″″″,
phoramides), and	and R″″″′ represent H, NH₂or any organic
Poly(monothiodi-	functional group wherein the number of
phosphoramides) (S—O	carbon atoms ranges from 0 to 40, optionally
Bidentates, S—O	having halogen or polarizing or water-
Tridentates, S—O	insolubilizing/solubilizing groups attached.
Tetradentates)	Ligand can also contain nonbinding N, O, S,
	or P atoms.
S—O Valence	(R—O—)(R′—O—)P(═S)—O—
Stabilizer #10:	P(═O)(—O—R″)(—O—R′″);
Monothiodi-	(R—O—)(R′—O—)P(═S)—
phosphoric Acids,	S—P(═O)(—O—R″)(—O—R′″);
Bis(monothioi-	(R—O—)(R′—O—)P(═S)—
phosphoric Acids),	O—P(═O)(—O—R″)(—O—R′″);
Poly(monothiodi-	(R—O—)(R′—O—)P(═S)—
phosphoric Acids), and	S—P(═O)(—O—R″)(—O—R′″); or
derivatives thereof	(R—S—)(R′—S—)P(═S)—
(S—O Bidentates,	S—P(═O)(—S—R″)(—S—R′″),
S—O Tridentates,	where R, R′, R″, R″′, R″″, R″″′, R″″″, and
S—O Tetradentates)	R″″″′ represent H, NH₂or any organic
	functional group wherein the number of
	carbon atoms ranges from 0 to 40, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S,
	or P atoms.
S—O Valence	RR′N⁺═C(OH)(SH), where R and R′
Stabilizer #11:	represent H, OH, SH, OR″ (R″═C₁-C₃₀
Monothiocarbamates,	alkyl or aryl), SR″ (R″═C₁-C₃₀alkyl
Bis(monothio-	or aryl), NH₂or any organic functional group
carbamates), and	wherein the number of carbon atoms ranges
Poly(monothiocarbamates)	from 0 to 40, optionally having halogen
(including N-	or polarizing or water-insolubilizing/
hydroxymonothio-	solubilizing groups attached. Ligand
carbamates and N-	can also contain nonbinding N, O, S,
mercaptomonothio-	or P atoms.
carbamates) (S—O
Bidentates, S—O
Tridentates, and S—O
Tetradentates)
Miscellaneous Valence	Hydroxo and oxo ligands bound directly to
Stabilizer #1:	the high valence metal ion.
Hydroxo and Oxo Ligands

N Valence Stabilizer #1: Examples of monoamines (N monodentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: ammonia; ethylamine; n-dodecylamine; octylamine; phenylamine; cyclohexylamine; diethylamine; dioctylamine; diphenylamine; dicyclohexylamine; azetidine; hexamethylenetetramine (Urotropin); aziridine; azepine; pyrrolidine; benzopyrrolidine; dibenzopyrrolidine; naphthopyrrolidine; piperidine; benzopiperidine; dibenzopiperidine; naphthopiperidine; azacycloheptane (hexamethyleneimine); aminonorbornane; adamantanamine; aniline; benzylamine; toluidine; phenethylamine; xylidine; cumidine; naphthylamine; polyalkylamines; polyanilines; and fluorenediamine.

N Valence Stabilizer #2: Examples of diamines (N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hydrazine; phenylhydrazine; 1,1-diphenylhydrazine; 1,2-diphenylhydrazine (hydrazobenzene); methanediamine; ethylenediamine (1,2-ethanediamine, en); trimethylenediamine (1,3-propanediamine); putrescine (1,4-butanediamine); cadaverine (1,5-pentanediamine); hexamethylenediamine (1,6-hexanediamine); 2,3-diaminobutane; stilbenediamine (1,2-diphenyl-1,2-ethanediamine); cyclohexane-1,2-diamine; cyclopentane-1,2-diamine; 1,3-diazacyclopentane; 1,3-diazacyclohexane; piperazine; benzopiperazine; dibenzopiperazine; naphthopiperazine; diazepine; thiadiazepine; oxodiazepine; sparteine (lupinidine); 2-(aminomethyl)azacyclohexane; 2-(aminomethyl)piperidine; 2-(aminomethyl)pyrrolidine; 2-(aminomethyl)azetidine; 2-(2-aminoethyl)aziridine; 1,2-diaminobenzene; benzidine; bis(2,2′-piperazino)-1,2-ethene; 1,4-diazabicyclo[2.2.2]octane; naphthylethylenediamine; and 1,2-dianilinoethane.

N Valence Stabilizer #3: Examples of triamines (N—N bidentates or N—N tridentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-(2-aminoethyl)-1,2-ethanediamine (dien, 2,2-tri); N-(2-aminoethyl)-1,3-propanediamine (2,3-tri); N-(3aminopropyl)-1,3-propanediamine (3,3-tri, dpt); N-(3-aminopropyl)-1,4-butanediamine (3,4-tri, spermidine); N-(2-aminoethyl)-1,4-butanediamine (2,4-tri); N-(6-hexyl)-1,6-hexanediamine (6,6-tri); 1,3,5-triaminocyclohexane (tach); 2-(aminomethyl)-1,3-propanediamine (tamm); 2-(aminomethyl)-2-methyl-1,3-propanediamine (tame); 2-(aminomethyl)-2-ethyl-1,3-propanediamine (tamp); 1,2,3-triaminopropane (tap); 2,3-(2-aminoethyl)aziridine; 2,4-(aminomethyl)azetidine; 2,5-(aminomethyl)pyrrolidine; 2,6-(aminomethyl)piperidine; di(2-aminobenzyl)amine; hexahydro-1,3,5-triazine; hexahydro-2,4,6-trimethyl-1,3,5-triazine; and 1,3,5-tris(aminomethyl)benzene.

N Valence Stabilizer #4: Examples of tetramines (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-(2-aminoethyl)-1,2-ethanediamine (2,2,2-tet, trien (triethylenetetramine)); N,N′-(2-aminoethyl)-1,3-propanediamine (2,3,2-tet, entnen); N,N′-(3-aminopropyl)-1,2-ethanediamine (3,2,3-tet, tnentn); N-(2-aminoethyl)-N′-(3-aminopropyl)-1,2-ethanediamine (2,2,3-tet); N-(2-aminoethyl)-N′-(3-aminopropyl)-1,3-propanediamine (3,3,2-tet); N,N′-(3-aminopropyl)-1,3-propanediamine (3,3,3-tet); N,N′-(3-aminopropyl)-1,4-butanediamine (3,4,3-tet, spermine); tri(aminomethyl)amine (tren); tri(2-aminoethyl)amine (trtn); tri(3-aminopropyl)amine (trbn); 2,2-aminomethyl-1,3-propanediamine (tam); 1,2,3,4-tetraminobutane (tab); N,N′-(2-aminophenyl)-1,2-ethanediamine; and N,N′-(2-aminophenyl)-1,3-propanediamine.

N Valence Stabilizer #5: Examples of pentamines (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-[N-(2-aminoethyl)-2-aminoethyl]-N′-(2-aminoethyl)-1,2-ethanediamine (2,2,2,2-pent, tetren); N-[N-(3-aminopropyl)-2-aminoethyl]-N′-(3-aminopropyl)-1,2-ethanediamine (3,2,2,3-pent); N-[N-(3-aminopropyl)-3-aminopropyl]-N ′-(3-aminopropyl)-1,3-propanediamine (3,3,3,3-pent, caldopentamine); N-[N-(2-aminobenzyl)-2-aminoethyl]-N′-(2-aminopropyl)-1,2-ethanediamine; N-[N-(2-aminoethyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine (trenen); and N-[N-(2-aminopropyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine (4-Me-trenen).

N Valence Stabilizer #6: Examples of hexamines (N—N bidentates, N—N tridentates, N—N tetradentates, or N—N—N—N—N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-[N-(2-aminoethyl)-2-aminoethyl]-1,2-ethanediamine (2,2,2,2,2-hex, linpen); N,N′-[N-(2-aminoethyl)-3-aminopropyl]-1,2-ethanediamine (2,3,2,3,2-hex); N,N,N′,N′-(2-aminoethyl)-1,2-ethanediamine (penten, ten); N,N,N′,N′-(2-aminoethyl)-1-methyl-1,2-ethanediamine (tpn, R-5-Me-penten); N,N,N′,N′-(2-aminoethyl)-1,3-propanediamine (ttn); N,N,N′,N′-(2-aminoethyl)-1,4-butanediamine (tbn); N,N,N′,N′-(2-aminoethyl)-1,3-dimethyl-1,3-propanediamine (R,R-tptn, R,S-tptn); N-(2-aminoethyl)-2,2-[N-(2-aminoethyl)aminomethyl-1-propaneamine (sen); and N-(3-aminopropyl)-2,2-[N-(3-aminopropyl)aminomethyl-1-propaneamine (stn).

N Valence Stabilizer #7a: Examples of 5-membered heterocyclic rings containing one nitrogen atom (N monodentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrole, oxazole, isoxazole, thiazole, isothiazole, azaphosphole, benzopyrroline, benzopyrrole (indole), benzoxazole, benzisoxazole, benzothiazole, benzisothiazole, benzazaphosphole, dibenzopyrroline, dibenzopyrrole (carbazole), dibenzoxazole, dibenzisoxazole, dibenzothiazole, dibenzisothiazole, naphthopyrroline, naphthopyrrole, naphthoxazole, naphthisoxazole, naphthothiazole, naphthisothiazole, naphthazaphosphole, and polypyrroles.

N Valence Stabilizer #7b: Examples of 5-membered heterocyclic rings containing two nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pyrazoline, imidazoline, imidazole (ia), pyrazole, oxadiazole, thiadiazole, diazaphosphole, benzopyrazoline, benzimidazoline, benzimidazole (azindole)(bia)(bz), benzopyrazole (indazole), benzothiadiazole (piazthiole), benzoxadiazole (benzofurazan), naphthopyrazoline, naphthimidazoline, naphthimidazole, naphthopyrazole, naphthoxadiazole, naphthothiadiazole, polybenzimidazole, and polyimidazoles (e.g. polyvinylimidazole (pvi)).

N Valence Stabilizer #7c: Examples of 5-membered heterocyclic rings containing three nitrogen atoms (N monodentates, N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: triazole, oxatriazole, thiatriazole, benzotriazole (bta), tolyltriazole (tt), naphthotriazole, and triazolophthalazine.

N Valence Stabilizer #7d: Examples of 5-membered heterocyclic rings containing four nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrazole.

N Valence Stabilizer #8a: Examples of 6-membered heterocyclic rings containing one nitrogen atom (N monodentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pyridine, picoline, lutidine, γ-collidine, oxazine, thiazine, azaphosphorin, quinoline, isoquinoline, benzoxazine, benzothiazine, benzazaphosphorin, acridine, phenanthridine, phenothiazine (dibenzothiazine), dibenzoxazine, dibenzazaphosphorin, benzoquinoline (naphthopyridine), naphthoxazine, naphthothiazine, naphthazaphosphorin, and polypyridines.

N Valence Stabilizer #8b: Examples of 6-membered heterocyclic rings containing two nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pyrazine, pyridazine, pyrimidine, oxadiazine, thiadiazine, diazaphosphorin, quinoxaline (benzopyrazine), cinnoline (benzo[c]pyridazine), quinazoline (benzopyrimidine), phthalazine (benzo[d]pyridazine), benzoxadiazine, benzothiadiazine, phenazine (dibenzopyrazine), dibenzopyridazine, naphthopyrazine, naphthopyridazine, naphthopyrimidine, naphthoxadiazine, naphthothiadiazine, and polyquinoxalines.

N Valence Stabilizer #8c: Examples of 6-membered heterocyclic rings containing three nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,3,5-triazine, 1,2,3-triazine, benzo-1,2,3-triazine, naphtho-1,2,3-triazine, oxatriazine, thiatriazine, melamine, and cyanuric acid.

N Valence Stabilizer #8d: Examples of 6-membered heterocyclic rings containing four nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrazine.

N Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(aminomethyl)-3-pyrroline; 2,5-(aminomethyl)-3-pyrroline; 2-(aminomethyl)pyrrole; 2,5-(aminomethyl)pyrrole; 3-(aminomethyl)isoxazole; 2-(aminomethyl)thiazole; 3-(aminomethyl)isothiazole; 2-(aminomethyl)indole; 2-aminobenzoxazole; 2-aininobenzothiazole (abt); 1,8-diaminocarbazole; 2-amino-6-methyl-benzothiazole (amebt); 2-amino-6-methoxybenzothiazole (ameobt), and 1,3-diiminoisoindoline.

N Valence Stabilizer #9b: Examples of 5-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminoimidazoline; 1-(3-aminopropyl)imidazoline; 2-aminoimidazole; 1-(3-aminopropyl)imidazole; 4-(2-aminoethyl)imidazole [histamine]; 1-alkyl-4-(2-aminoethyl)imidazole; 3-(2-aminoethyl)pyrazole; 3,5-(2-aminoethyl)pyrazole; 1-(aminomethyl)pyrazole; 2-aminobenzimidazole; 7-(2-aminoethyl)benzimidazole; 1-(3-aminopropyl)benzimidazole; 3-(2-aminoethyl)indazole; 3,7-(2-aminoethyl)indazole; 1-(aminomethyl)indazole; 7-aminobenzothiadiazole; 4-(2-aminoethyl)benzothiadiazole; 7-aminobenzoxadiazole; 4-(2-aminoethyl)benzoxadiazole; ethylenediaminetetra(1-pyrazolylmethane) [edtp]; methylenenitrilotris(2-(1-methyl)benzimidazole) [mntb] [tris(1-methyl-2-benzimidazolylmethane)amine]; bis(alkyl-1-pyrazolylmethane)amine; bis(alkyl-2-(1-pyrazolyl)ethane)amine; bis(N,N-(2-benzimidazolyl)-2-aminoethane)(2-benzimidazolylmethane)amine; bis(1-(3,5-dimethyl)pyrazolylmethane)phenylamine; tris(2-(1-(3,5-dimethyl)pyrazolyl)ethane)amine; 5-(dimethylamino)pyrazole; 5-(dimethylaminomethyl)pyrazole; 2-amino-1,3,4-thiadiazole; and 1-(2-aminoethyl)imidazoline.

N Valence Stabilizer #9c: Examples of 5-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N—N Tridentates, N—N—N—N Tetradentates, or N—N—N—N—N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-amino-1,2,4-triazole (ata); 3,5-diamino-1,2,4-triazole (dat); 5-amino-1,2,4-triazole; 3-(2-aminoethyl)-1,2,4-triazole; 5-(2-aminoethyl)-1,2,4-triazole; 3,5-(2-aminoethyl)-1,2,4-triazole; 1-(aminomethyl)-1,2,4-triazole; 3,5-(aminomethyl)-4-amino-1,2,4-triazole; 4-(2-aminoethyl)-1,2,3-triazole; 5-(2-aminoethyl)-1,2,3-triazole; 7-aminobenzotriazole; 1-(aminomethyl)-1,2,3-triazole; 1-(2-aminoethyl)-1,2,3-triazole; 4-(3-aminopropyl)benzotriazole; N-(benzotriazolylalkyl)amine; dibenzotriazole-1-ylalkylamine; bis(5-amino-1,2,4-triazol-3-yl); bis(5-amino-1,2,4-triazol-3-yl)alkanes; and 1-(aminomethyl)benzotriazole.

N Valence Stabilizer #9d: Examples of 5-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 5-(2-aminoethyl)-1H-tetrazole; 1-(aminomethyl)-1H-tetrazole; and 1-(2-aminoethyl)-1H-tetrazole.

N Valence Stabilizer #10a: Examples of 6-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminopyridine; 2,6-diaminopyridine; 2-(aminomethyl)pyridine; 2,6-(aminomethyl)pyridine; 2,6-(aminoethyl)pyridine; 2-amino-4-picoline; 2,6-diamino-4-picoline; 2-amino-3,5-lutidine; 2-aminoquinoline; 8-aminoquinoline; 2-aminoisoquinoline; acriflavine; 4-aminophenanthridine; 4,5-(aminomethyl)phenothiazine; 4,5-(aminomethyl)dibenzoxazine; 10-amino-7,8-benzoquinoline; bis(2-pyridylmethane)amine; tris(2-pyridyl)amine; bis(4(2-pyridyl)-3-azabutane)amine; bis(N,N-(2-(2-pyridyl)ethane)aminomethane)amine; 4-(N,N-dialkylaminomethyl)morpholine; 6-aminonicotinic acid; 8-aminoacridine; and 2-hydrazinopyridine.

N Valence Stabilizer #10b: Examples of 6-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminopyrazine; 2,6-diaminopyrazine; 2-(aminomethyl)pyrazine; 2,6-(aminomethyl)pyrazine; 3-(aminomethyl)pyridazine; 3,6-(aminomethyl)pyridazine; 3,6-(2-aminoethyl)pyridazine; 1-aminopyridazine; 1-(aminomethyl)pyridazine; 2-aminopyrimidine; 1-(2-aminoethyl)pyrimidine; 2-aminoquinoxaline; 2,3-diaminoquinoxaline; 2-aminocinnoline; 3-aminocinnoline; 3-(2-aminoethyl)cinnoline; 3,8-(2-aminoethyl)cinnoline; 2-aminoquinazoline; 1-(2-aminoethyl)quinazoline; 1-aminophthalazine; 1,4-(2-aminoethyl)phthalazine; 1,8-(aminomethyl)phenazine; 2-amino-4,6-dimethylpyrimidine (admp); dihydralazine; and hydralazine.

N Valence Stabilizer #10c: Examples of 6-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-amino-1,3,5-triazine; 2-(aminomethyl)-1,3,5-triazine; 2,6-(aminomethyl)-1,3,5-triazine; 1-(3-aminopropyl)-1,3,5-triazine; 1,5-(3-aminopropyl)-1,3,5-triazine, polymelamines; melamine; and altretamine.

N Valence Stabilizer #10d: Examples of 6-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3,6-(2-aminoethyl)-1,2,4,5-tetrazine; 3,6-(1,3-diamino-2-propyl)-1,2,4,5-tetrazine; and 4,6-(aminomethyl)-1,2,3,5-tetrazine.

N Valence Stabilizer #11a: Examples of 5-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-3-pyrroline; 2,2′-bi-2-pyrroline; 2,2′-bi-1-pyrroline; 2,2′-bipyrrole; 2,2′,2″-tripyrrole; 3,3′-biisoxazole; 2,2′-bioxazole; 3,3′-biisothiazole; 2,2′-bithiazole; 2,2′-biindole; 2,2′-bibenzoxazole; 2,2′-bibenzothiazole; bilirubin; biliverdine; and 7-azaindole.

N Valence Stabilizer #11b: Examples of 5-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-2-imidazoline [2,2′-bi-2-imidazolinyl][bimd]; 2,2′-biimidazole [2,2′-biimidazolyl][biimH₂]; 5,5′-bipyrazole; 3,3′-bipyrazole; 4,4′-bipyrazole [4,4′-bipyrazolyl][bpz]; 2,2′-bioxadiazole; 2,2′-bithiadiazole; 2,2′-bibenzimidazole; 7,7′-biindazole; 5,5′-bibenzofurazan; 5,5′-bibenzothiadiazole; bis-1,2-(2=benzimidazole)ethane; bis(2-benzimidazole)methane; 1,2-(2-imidazolyl)benzene; 2-(2-thiazolyl)benzimidazole; 2-(2-imidazolyl)benzimidazole; benzimidazotriazine; 4-azabenzimidazole; and 2,6-bis(2-benzimidazolyl)pyridine.

N Valence Stabilizer #11c: Examples of 5-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 5,5′-bi-1,2,4-triazole [btrz]; 3,3′-bi-1,2,4-triazole; 1,1′-bi-1,2,4-triazole; 1,1′-bi-1,2,3-triazole; 5,5′-bi-1,2,3-triazole; 7,7′-bibenzotriazole; 1,1′-bibenzotriazole; bis(pyridyl)aminotriazole (pat); and 8-azaadenine.

N Valence Stabilizer #11d: Examples of 5-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 5,5′-bi-1H-tetrazole; and 1,1′-bi-1H-tetrazole.

N Valence Stabilizer #12a: Examples of 6-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bipyridine [bipy]; 2,2′,2″-tripyridine [terpyridine] [terpy]; 2,2′,2″,2′″-tetrapyridine [tetrapy]; 6,6′-bi-2-picoline; 6,6′-bi-3-picoline; 6,6′-bi-4-picoline; 6,6′-bi-2,3-lutidine; 6,6′-bi-2,4-lutidine; 6,6′-bi-3,4-lutidine; 6,6′-bi-2,3,4-collidine; 2,2′-biquinoline; 2,2′-biisoquinoline; 3,3′-bibenzoxazine; 3,3′-bibenzothiazine; 1,10-phenanthroline [phen]; 1,8-naphthyridine; bis-1,2-(6-(2,2′-bipyridyl))ethane; bis-1,3-(6-(2,2′-bipyridyl))propane; 3,5-bis(3-pyridyl)pyrazole; 3,5-bis(2-pyridyl)triazole; 1,3-bis(2-pyridyl)-1,3,5-triazine; 1,3-bis(2-pyridyl)-5-(3-pyridyl)-1,3,5-triazine; 2,7-(N,N′-di-2-pyridyl)diaminobenzopyiroline; 2,7-(N,N′-di-2-pyridyl)diaminophthalazine; 2,6-di-(2-benzothiazolyl)pyridine; triazolopyrimidine; 2-(2-pyridyl)imidazoline; 7-azaindole; i-(2-pyridyl)pyrazole; (1-imidazolyl)(2-pyridyl)methane; 4,5-bis(N,N′-(2-(2-pyridyl)ethyl)iminomethyl)imidazole; bathophenanthroline; 4-(2-benzimidazolyl)quinoline; 1,2-bis(2-pyridyl)ethane; 4,4′-diphenyl-2,2′-dipyridyl; neocuproine; nicotine; and nornicotine.

N Valence Stabilizer #12b: Examples of 6-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bipyrazine; 2,2′,2″-tripyrazine; 6,6′-bipyridazine; bis(3-pyridazinyl)methane; 1,2-bis(3-pyridazinyl)ethane; 2,2′-bipyrimidine; 2,2′-biquinoxaline; 8,8′-biquinoxaline; bis(3-cinnolinyl)methane; bis(3-cinnolinyl)ethane; 8,8′-bicinnoline; 2,2′-biquinazoline; 4,4′-biquinazoline; 8,8′-biquinazoline; 2,2′-biphthalazine; 1,1′-biphthalazine; 2-(2-pyridyl)benzimidazole; 8-azapurine; purine; adenine; guanine; hypoxanthine; 2,6-bis(N,N′-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine; 2-(N-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine; adenine (aminopurine); purine; and 2,3-bis(2-pyridyl)pyrazine.

N Valence Stabilizer #12c: Examples of 6-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,3,5-triazine; 2,2′,2″-tri-1,3,5-triazine; 4,4′-bi-1,2,3-triazine; and 4,4′-bibenzo-1,2,3-triazine; 2,4,6-tris(2-pyridyl)-1,3,5-triazine; and benzimidazotriazines.

N Valence Stabilizer #12d: Examples of 6-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3,3′-bi-1,2,4,5-tetrazine; and 4,4′-bi-1,2,3,5-tetrazine.

N Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacyclobutane ([4]aneN₂); diazacyclopentane ([5]aneN₂); diazacyclohexane ([6]aneN₂); diazacycloheptane ([7]aneN₂); diazacyclooctane ([8]aneN₂); piperazine; benzopiperazine; diazacyclobutene ([4]eneN₂); diazacyclopentene ([5]eneN₂); diazacyclohexene ([6]eneN₂); diazacycloheptene ([7]eneN₂); diazacyclooctene ([8]eneN₂); diazacyclobutadiene ([4]dieneN₂); diazacyclopentadiene ([5]dieneN₂); diazacyclohexadiene ([6]dieneN₂); diazacycloheptadiene ([7]dieneN₂); and diazacyclooctadiene ([8]dieneN₂).

N Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: triazacyclohexane (including hexahydro-1,3,5-triazine)([6]aneN₃); triazacycloheptane ([7]aneN₃); triazacyclooctane ([8]aneN₃); triazacyclononane ([9]aneN₃); triazacyclodecane ([10]aneN₃); triazacycloundecane ([11]aneN₃); triazacyclododecane ([12]aneN₃); triazacyclohexene ([6]eneN₃); triazacycloheptene ([7]eneN₃); triazacyclooctene ([8]eneN₃); triazacyclononene ([9]eneN₃); triazacyclodecene ([10]eneN₃); triazacycloundecene ([11]eneN₃); triazacyclododecene ([12]eneN₃); triazacyclohexatriene ([6]trieneN₃); triazacycloheptatriene ([7]trieneN₃); triazacyclooctatriene ([8]trieneN₃); triazacyclononatriene ([9]trieneN₃); triazacyclodecatriene ([10]trieneN₃); triazacycloundecatriene ([11]trieneN₃); and triazacyclododecatriene ([12]trieneN₃).

N Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetraazacyclooctane ([8]aneN₄); tetraazacyclononane ([9]aneN₄); tetraazacyclodecane ([10]aneN₄); tetraazacycloundecane ([11]aneN₄); tetraazacyclododecane ([12]aneN₄); tetraazacyclotridecane ([13]aneN₄); tetraazacyclotetradecane ([14]aneN₄); tetraazacyclopentadecane ([15]aneN₄); tetraazacyclohexadecane ([16]aneN₄); tetraazacycloheptadecane ([17]aneN₄); tetraazacyclooctadecane ([18]aneN₄); tetraazacyclononadecane ([19]aneN₄); tetraazacycloeicosane ([20]aneN₄); tetraazacyclooctadiene ([8]dieneN₄); tetraazacyclononadiene ([9]dieneN₄); tetraazacyclodecadiene ([10]dieneN₄); tetraazacycloundecadiene ([11]dieneN₄); tetraazacyclododecadiene ([12]dieneN₄); tetraazacyclotridecadiene ([13]dieneN₄); tetraazacyclotetradecadiene ([14]dieneN₄); tetraazacyclopentadecadiene ([15]dieneN₄); tetraazacyclohexadecadiene ([16]dieneN₄); tetraazacycloheptadecadiene ([17]dieneN₄); tetraazacyclooctadecadiene ([18]dieneN₄); tetraazacyclononadecadiene ([19]dieneN₄); tetraazacycloeicosadiene ([20]dieneN₄); tetraazacyclooctatetradiene ([8]tetradieneN₄); tetraazacyclononatetradiene ([9]tetradieneN₄); tetraazacyclodecatetradiene ([10]tetradieneN₄); tetraazacycloundecatetradiene ([11]tetradieneN₄); tetraazacyclododecatetradiene ([12]tetradieneN₄); tetraazacyclotridecatetradiene ([13]tetradieneN₄); tetraazacyclotetradecatetradiene ([14]tetradieneN₄); tetraazacyclopentadecatetradiene ([15]tetradieneN₄); tetraazacyclohexadecatetradiene ([16]tetradieneN₄); tetraazacycloheptadecatetradiene ([17]tetradieneN₄); tetraazacyclooctadecatetradiene ([18]tetradieneN₄); tetraazacyclononadecatetradiene ([19]tetradieneN₄); and tetraazacycloeicosatetradiene ([20]tetradieneN₄).

N Valence Stabilizer #13d: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexaazacyclododecane ([12]aneN₆); hexaazacyclotridecane ([13]aneN₆); hexaazacyclotetradecane ([14]aneN₆); hexaazacyclopentadecane ([15]aneN₆); hexaazacyclohexadecane ([16]aneN₆); hexaazacycloheptadecane ([17]aneN₆); hexaazacyclooctadecane ([18]aneN₆); hexaazacyclononadecane ([19]aneN₆); hexaazacycloeicosane ([20]aneN₆); hexaazacycloheneicosane ([21]aneN₆); hexaazacyclodocosane ([22]aneN₆); hexaazacyclotricosane ([23]aneN₆); hexaazacyclotetracosane ([24]aneN₆); hexaazacyclododecatriene ([12]trieneN₆); hexaazacyclotridecatriene ([13]trieneN₆); hexaazacyclotetradecatriene ([14]trieneN₆); hexaazacyclopentadecatriene ([15]trieneN₆); hexaazacyclohexadecatriene ([16]trieneN₆); hexaazacycloheptadecatriene ([17]trieneN₆); hexaazacyclooctadecatriene ([18]trieneN₆); hexaazacyclononadecatriene ([19]trieneN₆); hexaazacycloeicosatriene ([20]trieneN₆); hexaazacycloheneicosatriene ([21]trieneN₆); hexaazacyclodocosatriene ([22]trieneN₆); hexaazacyclotricosatriene ([23]trieneN₆); and hexaazacyclotetracosatriene ([24]trieneN₆).

N Valence Stabilizer #13e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: octaazacyclohexadecane ([16]aneN₈); octaazacycloheptadecane ([17]aneN₈); octaazacyclooctadecane ([18]aneN₈); octaazacyclononadecane ([19]aneN₈); octaazacycloeicosane ([20]aneN₈); octaazacycloheneicosane ([21]aneN₈); octaazacyclodocosane ([22]aneN₈); octaazacyclotricosane ([23]aneN₈); octaazacyclotetracosane ([24]aneN₈); octaazacyclohexadecatetradiene ([16]tetradieneN₈); octaazacycloheptadecatetradiene ([17]tetradieneN₈); octaazacyclooctadecatetradiene ([18]tetradieneN₈); octaazacyclononadecatetradiene ([19]tetradieneN₈); octaazacycloeicosatetradiene ([20]tetradieneN₈); octaazacycloheneicosatetradiene ([21]tetradieneN₈); octaazacyclodocosatetradiene ([22]tetradieneN₈); octaazacyclotricosatetradiene ([23]tetradieneN₈); and octaazacyclotetracosatetradiene ([24]tetradieneN₈).

N Valence Stabilizer #13f: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchratcs) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: decaazacycloeicosane ([20]aneN₀); decaazacycloheneicosane ([21]aneN₁₀); decaazacyclodocosane ([22]aneN₁₀); decaazacyclotricosane ([23]aneN₁₀); decaazacyclotetracosane ([24]aneN₁₀); decaazacyclopentacosane ([25]aneN₁₀); decaazacyclohexacosanc ([26]aneN₁₀); decaazacycloheptacosane ([27]aneN₁₀); decaazacyclooctacosane ([28]aneN₁₀); decaazacyclononacosane ([29]aneN₁₀); decaazacyclotriacontane ([30]aneN₁₀); decaazacycloeicosapentadiene ([20]pentadieneN₁₀); decaazacycloheneicosapentadiene ([21]pentadieneN₁₀); decaazacyclodocosapentadiene ([22]pentadieneN₁₀); decaazacyclotricosapentadiene ([23]pentadieneN₁₀); decaazacyclotetracosapentadiene ([24]pentadieneN₁₀); decaazacyclopentacosapentadiene ([25]pentadieneN₁₀); decaazacyclohexacosapentadiene ([26]pentadieneN₁₀); decaazacycloheptacosapentadiene ([27]pentadieneN₁₀); decaazacyclooctacosapentadiene ([28]pentadieneN₁₀); decaazacyclononacosapentadiene ([29]pentadieneN₁₀); and decaazacyclotriacontapentadiene ([30]pentadieneN₁₀).

N Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: porphyrins (including tetraphenylporphine (tpp); “picket fence” porphyrins, “picket tail” porphyrins, “bispocket” porphyrins, “capped” porphyrins, cyclophane porphyrins, “pagoda” porphyrins, “pocket” porphyrins, “pocket tail” porphyrins, cofacial diporphyrins, “strapped” porphyrins, “hanging base” porphyrins, bridged porphyrins, chelated mesoporphyrins, homoporphyrins, chlorophylls, and pheophytins); porphodimethanes; porphyrinogens; chlorins; bacteriochlorins; isobacteriochlorins; corroles; corrins and corrinoids; didehydrocorrins; tetradehydrocorrins; hexadehydrocorrins; octadehydrocorrins; tetraoxazoles; tetraisooxazoles; tetrathiazoles; tetraisothiazoles; tetraazaphospholes; tetraimidazoles; tetrapyrazoles; tetraoxadiazoles; tetrathiadiazoles; tetradiazaphospholes; tetratriazoles; tetraoxatriazoles; tetrathiatriazoles; coproporphyrin; etioporphyrin; and hematoporphyrin.

N Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexaphyrins (hexapyrroles); hexaoxazoles; hexaisooxazoles; hexathiazoles; hexaisothiazoles; hexaazaphospholes; hexaimidazoles; hexapyrazoles; hexaoxadiazoles; hexathiadiazoles; hexadiazaphospholes; hexatriazoles; hexaoxatriazoles; and hexathiatriazoles.

N Valence Stabilizer #14c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: octaphyrins (octapyrroles); octaoxazoles; octaisooxazoles; octathiazoles; octaisothiazoles; octaazaphospholes; octaimidazoles; octapyrazoles; octaoxadiazoles; octathiadiazoles; octadiazaphospholes; octatriazoles; octaoxatriazoles; and octathiatriazoles.

N Valence Stabilizer #14d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: decaphyrins (decapyrroles); decaoxazoles; decaisooxazoles; decathiazoles; decaisothiazoles; decaazaphospholes; decaimidazoles; decapyrazoles; decaoxadiazoles; decathiadiazoles; decadiazaphospholes; decatriazoles; decaoxatriazoles; and decathiatriazoles.

N Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: porphyrazines; octahydrodiazaporphyrins; phthalocyanines; naphthalocyanines; anthracocyanines; and tetraazaporphyrins

N Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazahexaphyrins; tetraazahexaphyrins; hexaazahexaphyrins; diazahexapyrazoles; tetraazahexapyrazoles; hexaazahexapyrazoles; diazahexaimidazoles; tetraazahexaimidazoles; and hexaazahexaimidazoles.

N Valence Stabilizer #15c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazaoctaphyrins; tetraazaoctaphyrins; hexaazaoctaphyrins; octaazaoctaphyrins; diazaoctapyrazoles; tetraazaoctapyrazoles; hexaazaoctapyrazoles; octaazaoctapyrazoles; diazaoctaimidazoles; tetraazaoctaimidazoles; hexaazaoctaimidazoles; and octaazaoctaimidazoles.

N Valence Stabilizer #15d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazadecaphyrins; tetraazadecaphyrins; hexaazadecaphyrins; octaazadecaphyrins; decaazadecaphyrins; diazadecapyrazoles; tetraazadecapyrazoles; hexaazadecapyrazoles; octaazadecapyrazoles; decaazadecapyrazoles; diazadecaimidazoles; tetraazadecaimidazoles; hexaazadecaimidazoles; octaazadecaimidazoles; and decaazadecaimidazoles.

N Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclotetrapyridines; cyclotetraoxazines; cyclotetrathiazines; cyclotetraphosphorins; cyclotetraquinolines; cyclotetrapyrazines; cyclotetrapyridazines; cyclotetrapyrimidines; cyclotetraoxadiazines; cyclotetrathiadiazines; cyclotetradiazaphosphorins; cyclotetraquinoxalines; cyclotetratriazines; cyclotetrathiatriazines; and cyclotetraoxatriazines.

N Valence Stabilizer #16b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclosexipyridines; cyclosexioxazines; cyclosexithiazines; cyclosexiphosphorins; cyclosexiquinolines; cyclosexipyrazines; cyclosexipyridazines; cyclosexipyrimidines; cyclosexioxadiazines; cyclosexithiadiazines; cyclosexidiazaphosphorins cyclosexiquinoxalines; cyclosexitriazines; cyclosexithiatriazines; and cyclosexioxatriazines.

N Valence Stabilizer #16c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclooctapyridines; cyclooctaoxazines; cyclooctathiazines; cyclooctaphosphorins; cyclooctaquinolines; cyclooctapyrazines; cyclooctapyridazines; cyclooctapyrimidines; cyclooctaoxadiazines; cyclooctathiadiazines; cyclooctadiazaphosphorins; cyclooctaquinoxalines; cyclooctatriazines; cyclooctathiatriazines; and cyclooctaoxatriazines.

N Valence Stabilizer #16d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclodecapyridines; cyclodecaoxazines; cyclodecathiazines; cyclodecaphosphorins; cyclodecaquinolines; cyclodecapyrazines; cyclodecapyridazines; cyclodecapyrimidines; cyclodecaoxadiazines; cyclodecathiadiazines; cyclodecadiazaphosphorins; cyclodecaquinoxalines; cyclodecatriazines; cyclodecathiatriazines; and cyclodecaoxatriazines.

N Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacyclotetrapyridines; tetraazacyclotetrapyridines; diazacyclotetraquinolines; tetraazacyclotetraquinolines; diazacyclotetrapyrazines; tetraazacyclotetrapyrazines; diazacyclotetrapyridazines; tetraazacyclotetrapyridazines; diazacyclotetrapyrimidines; tetraazacyclotetrapyrimidines; diazacyclotetratriazines; and tetraazacyclotetratriazines.

N Valence Stabilizer #17b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacyclosexipyridines; triazacyclosexipyridines; diazacyclosexiquinolines; triazacyclosexiquinolines; diazacyclosexipyrazines; triazacyclosexipyrazines; diazacyclosexipyridazines; triazacyclosexipyridazines; diazacyclosexipyrimidines; triazacyclosexipyrimidines; diazacyclosexitriazines; and triazacyclosexitriazines.

N Valence Stabilizer #17c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacyclooctapyridines; tetraazacyclooctapyridines; diazacyclooctaquinolines; tetraazacyclooctaquinolines; diazacyclooctapyrazines; tetraazacyclooctapyrazines; diazacyclooctapyridazines; tetraazacyclooctapyridazines; diazacyclooctapyrimidines; tetraazacyclooctapyrimidines; diazacyclooctatriazines; and tetraazacyclooctatriazines.

N Valence Stabilizer #17d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacyclodecapyridines; pentaazacyclodecapyridines; diazacyclodecaquinolines; pentaazacyclodecaquinolines; diazacyclodecapyrazines; pentaazacyclodecapyrazines; diazacyclodecapyridazines; pentaazacyclodecapyridazines; diazacyclodecapyrimidines; pentaazacyclodecapyrimidines; diazacyclodecatriazines; and pentaazacyclodecatriazines.

N Valence Stabilizer #18: Examples of amidines and diamidines (N—N bidentates or N—N Tetradentates) that meet the requirements for use as ““wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-dimethylformamidine; N,N′-diethylformamidine; N,N′-diisopropylformamidine; N,N′-dibutylformamidine; N,N′-diphenylformamidine; N,N′-dibenzylformamidine; N,N′-dinaphthylformamidine; N,N′-dicyclohexylformamidine; N,N′-dinorbornylformamidine; N,N′-diadamantylformamidine; N,N′-dianthraquinonylformamidine; N,N′-dimethylacetamidine; N,N′-diethylacetamidine; N,N′-diisopropylacetamidine; N,N′-dibutylacetamidine; N,N′-diphenylacetamidine; N,N′-dibenzylacetamidine; N,N′-dinaphthylacetamidine; N,N′-dicyclohexylacetamidine; N,N′-dinorbornylacetamidine; N,N′-diadamantylacetamidine; N,N′-dimethylbenzamidine; N,N′-diethylbenzamidine; N,N′-diisopropylbenzamidine; N,N′-dibutylbenzamidine; N,N′-diphenylbenzamidine; N,N′-dibenzylbenzamidine; N,N′-dinaphthylbenzamidine; N,N′-dicyclohexylbenzamidine; N,N′-dinorbornylbenzamidine; N,N′-diadamantylbenzamidine; N,N′-dimethyltoluamidine; N,N′-diethyltoluamidine; N,N′-diisopropyltoluamidine; N,N′-dibutyltoluamidine; N,N′-diphenyltoluamidine; N,N′-dibenzyltoluamidine; N,N′-dinaphthyltoluamidine; N,N′-dicyclohexyltoluamidine; N,N′-dinorbornyltoluamidine; N,N′-diadamantyltoluamidine; oxalic diamidine; malonic diamidine; succinic diamidine; glutaric diamidine; adipic diamidine; pimelic diamidine; suberic diamidine; phthalic diamidine; terephthalic diamidine; isophthalic diamidine; piperazine diamidine; 2-iminopyrrolidine; 2-iminopiperidine; amidinobenzamide; benzamidine; chloroazodin; and debrisoquin.

N Valence Stabilizer #19: Examples of biguamides (imidodicarbonimidic diamides), biguanidines, imidotricarbonimidic diamides, imidotetracarbonimidic diamides, dibiguamides, bis(biguanidines), polybiguamides, and poly(biguanidines) (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: biguamide (bigH); biguanidine, methylbiguamide; ethylbiguamide; isopropylbiguamide; butylbiguamide; benzylbiguamide; phenylbiguamide; tolylbiguamide; naphthylbiguamide; cyclohexylbiguamide; norbornylbiguamide; adamantylbiguamide; dimethylbiguamide; diethylbiguamide; diisopropylbiguamide; dibutylbiguamide; dibenzylbiguamide; diphenylbiguamide; ditolylbiguamide; dinaphthylbiguamide; dicyclohexylbiguamide; dinorbornylbiguamide; diadamantylbiguamide; ethylenedibiguamide; propylenedibiguamide; tetramethylenedibiguamide; pentamethylenedibiguamide; hexamethylenedibiguamide; heptamethylenedibiguamide; octamethylenedibiguamide; phenylenedibiguamide; piperazinedibiguamide; oxalyldibiguamide; malonyldibiguamide; succinyldibiguamide; glutaryldibiguamide; adipyldibiguamide; pimelyldibiguamide; suberyldibiguamide; phthalyldibiguamide; paludrine; polyhexamethylene biguamide; 2-guanidinothiazole; 2-guanidinooxazole; 2-guanidinoimidazole; 3-guanidinopyrazole; 3-guanidino-1,2,4-triazole; 5-guanidinotetrazole; alexidine; buformin; and moroxydine.

N Valence Stabilizer #20: Examples of diamidinomethanes, bis(diamidinomethanes), and poly(diamidinomethanes) (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diamidinomethane; N-methyldiamidinomethane; N-ethyldiamidinomethane; N-isopropyldiamidinomethane; N-butyldiamidinomethane; N-benzyldiamidinomethane; N-phenyldiamidinomethane; N-tolyldiamidinomethane; N-naphthyldiamidinomethane; N-cyclohexyldiamidinomethane; N-norbornyldiamidinomethane; N-adamantyldiamidinomethane; dimethyldiamidinomethane; diethyldiamidinometbane; diisopropyldiamidinomethane; dibutyldiamidinomethane; dibenzyldiamidinomethane; diphenyldiamidinomethane; ditolyldiamidinomethane; dinaphthyldiamidinomethane; dicyclohexyldiamidinomethane; dinorbornyldiamidinomethane; diadamantyldiamidinomethane; ethylenebisdiamidinomethane; propylenebisdiamidinomethane; tetramethylenebisdiamidinomethane; pentamethylenebisdiamidinomethane; hexamethylenebisdiamidinomethane; heptamethylenebisdiamidinomethane; octamethylenebisdiamidinomethane; phenylenebisdiamidinomethane; piperazinebisdiamidinomethane; oxalylbisdiamidinomethane; malonylbisdiamidinomethane; succinylbisdiamidinomethane; glutarylbisdiamidinomethane; phthalylbisdiamidinomethane; 2-ainidinomethylthiazole; 2-amidinomethyloxazole; 2-amidinomethylimidazole; 3-amidinomethylpyrazole; 3-amidinomethyl-1,2,4-triazole; and 5-amidinomethyltetrazole.

N Valence Stabilizer #21: Examples of imidoylguanidines, amidinoguanidines, bis(imidoylguanidines), bis(amidinoguanidines), poly(imidoylguanidines), and poly(amidinoguanidines) (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetimidoylguanidine; amidinoguanidine, benzimidoylguanidine; cyclohexylimidoylguanidine; pentafluorobenzimidoylguanidine; 2-N-imidoylaminothiazole; 2-N-imidoylaminooxazole; 2-N-imidoylaminoimidazole; 3-N-imidoylaminopyrazole; 3-N-imidoylamino-1,2,4-triazole; and 5-N-imidoylaminotetrazole.

N Valence Stabilizer #22: Examples of diformamidine oxides (dicarbonimidic diamides), tricarbonimidic diamides, tetracarbonimidic diamides, bis(diformamidine oxides), and poly(diformamidine oxides) (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diformamidine oxide; methyldiformamidine oxide; ethyldiformamidine oxide; isopropyldiformamidine oxide; butyldiformamidine oxide; benzyldiformamidine oxide; phenyldiformamidine oxide; tolyldiformamidine oxide; naphthyldiformamidine oxide; cyclohexyldiformamidine oxide; norbornyldiformamidine oxide; adamantyldiformamidine oxide; dimethyldiformamidine oxide; diethyldiformamidine oxide; diisopropyldiformamidine oxide; dibutyldiformamidine oxide; dibenzyldiformamidine oxide; diphenyldiformamidine oxide; ditolyldiformamidine oxide; dinaphthyldiformamidine oxide; dicyclohexyldiformamidine oxide; dinorbornyldiformamidine oxide; diadamantyldiformamidine oxide; 2-O-amidinohydroxythiazole; 2-O-amidinohydroxyoxazole; 2-O-amidinohydroxyimidazole; 3-O-amidinohydroxypyrazole; 3-O-amidinohydroxy-1,2,4-triazole; and 5-O-amidinohydroxytetrazole.

N Valence Stabilizer #23: Examples of diformamidine sulfides (thiodicarbonimidic diamides), thiotricarbonimidic diamides, thiotetracarbonimidic diamides, bis(diformamidine sulfides), and poly(diformamidine sulfides) (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diformamidine sulfide; methyldiformamidine sulfide; ethyldiformamidine sulfide; isopropyldiformamidine sulfide; butyldiformamidine sulfide; benzyldiformamidine sulfide; phenyldiformamidine sulfide; tolyldiformamidine sulfide; naphthyldiformamidine sulfide; cyclohexyldiformamidine sulfide; norbornyldiformamidine sulfide; adamantyldiformamidine sulfide; dimethyldiformamidine sulfide; diethyldiformamidine sulfide; diisopropyldiformamidine sulfide; dibutyldiformamidine sulfide; dibenzyldiformamidine sulfide; diphenyldiformamidine sulfide; ditolyldiformamidine sulfide; dinaphthyldiformamidine sulfide; dicyclohexyldiformamidine sulfide; dinorbornyldiformamidine sulfide; diadamantyldiformamidine sulfide; phenylthiobisformamidine; 2-S-amidinomercaptothiazole; 2-S-amidinomercaptooxazole; 2-S-amidinomercaptoimidazole; 3-S-amidinomercaptopyrazole; 3-S-amidinomercapto-1,2,4-triazole; and 5-S-amidinomercaptotetrazole.

N Valence Stabilizer #24: Examples of imidodicarbonimidic acids, diimidodicarbonimidic acids, imidotricarbonimidic acids, imidotetracarbonimidic acids, and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: imidodicarbonimidic acid, diimidodicarbonimidic acid, imidotricarbonimidic acid, imidotetracarbonimidic acid; O-methylimidodicarbonimidic acid; O-ethylimidodicarbonimidic acid; O-isopropylimidodicarbonimidic acid; O-phenylimidodicarbonimidic acid; O-benzylimidodicarbonimidic acid; O-cyclohexylimidodicarbonimidic acid; O-naphthylimidodicarbonimidic acid; O-norbornylimidodicarbonimidic acid; O-adamantylimidodicarbonimidic acid; O,O′-dimethylimidodicarbonimidic acid; O,O′-diethylimidodicarbonimidic acid; O,O′-diisopropylimidodicarbonimidic acid; O,O′-diphenylimidodicarbonimidic acid; O,O′-dibenzylimidodicarbonimidic acid; O,O′-dicyclohexylimidodicarbonimidic acid; O,O′-dinaphthylimidodicarbonimidic acid; O,O′-dinorbornylimidodicarbonimidic acid; and O,O′-diadamantylimidodicarbonimidic acid.

N Valence Stabilizer #25: Examples of thioimidodicarbonimidic acids, thiodiimidodicarbonimidic acids, thioimidotricarbonimidic acids, thioimidotetracarbonimidic acids, and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thioimidodicarbonimidic acid, thiodiimidodicarbonimidic acid, thioimidotricarbonimidic acid, thioimidotetracarbonimidic acid; O-methylthioimidodicarbonimidic acid; O-ethylthioimidodicarbonimidic acid; O-isopropylthioimidodicarbonimidic acid; O-phenylthioimidodicarbonimidic acid; O-benzylthioimidodicarbonimidic acid; O-cyclohexylthioimidodicarbonimidic acid; O-naphthylthioimidodicarbonimidic acid; O-norbornylthioimidodicarbonimidic acid; O-adamantylthioimidodicarbonimidic acid; O,O′-dimethylthioimidodicarbonimidic acid; O,O′-diethylthioimidodicarbonimidic acid; O,O′-diisopropylthioimidodicarbonimidic acid; O,O′-diphenylthioimidodicarbonimidic acid; O,O′-dibenzylthioimidodicarbonimidic acid; O,O′-dicyclohexylthioimidodicarbonimidic acid; O,O′-dinaphthylthioimidodicarbonimidic acid; O,O′-dinorbornylthioimidodicarbonimidic acid; and O,O′-diadamantylthioimidodicarbonimidic acid.

N Valence Stabilizer #26: Examples of diimidoylimines, diimidoylhydrazides, bis(diimidoylimines), bis(diimidoylhydrazides), poly(diimidoylimines), and poly(diimidoylhydrazides) (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diacetimidoylimine; dibenzimidoylimine; and dicyclohexylimidoylimine.

N Valence Stabilizer #27: Examples of imidosulfamides, diimidosulfamides, bis(imidosulfamides), bis(diimidosulfamides), poly(imidosulfamides), and poly(diimidosulfamides) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: imidosulfamidic acid, diimidosulfamidic acid; O-phenylimidosulfamide; O-benzylimidosulfamide; N-phenylimidosulfamide; N-benzylimidosulfamide; O-phenyldiimidosulfamide; O-benzyldiimidosulfamide; N-phenyldiimidosulfamide; and N-benzyldiimidosulfamide.

N Valence Stabilizer #28: Examples of phosphoramidimidic triamides, bis(phosphoramidimidic triamides), and poly(phosphoramidimidic triamides) and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoramidimidic triamide; N-phenylphosphoramidimidic triamide; N-benzylphosphoramidimidic triamide; N-naphthylphosphoramidimidic triamide; N-cyclohexylphosphoramidimidic triamide; N-norbornylphosphoramidimidic triamide; N,N′-diphenylphosphorainidimidic triamide; N,N′-dibenzylphosphoramidimidic triamide; N,N′-dinaphthylphosphoramidimidic triamide; N,N′-dicyclohexylphosphoramidimidic triamide; and N,N′-dinorbornylphosphoramidimidic triamide.

N Valence Stabilizer #29: Examples of phosphoramidimidic acid, phosphorodiamidimidic acid, bis(phosphoramidimidic acid), bis(phosphorodiamidimidic acid), poly(phosphoramidimidic acid), poly(phosphorodiamidimidic acid), and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoramidimidic acid, phosphorodiamidimidic acid, O-phenylphosphoramidimidic acid; O-benzylphosphoramidimidic acid; O-naphthylphosphoramidimidic acid; O-cyclohexylphosphoramidimidic acid; O-norbornylphosphorainidimidic acid; O,O′-diphenylphosphoramidimidic acid; O,O′-dibenzylphosphoramidimidic acid; O,O′-dinaphthylphosphoramidimidic acid; O,O′-dicyclohexylphosphoramidimidic acid; and O,O′-dinorbornylphosphoramidimidic acid.

N Valence Stabilizer #30: Examples of phosphoramidimidodithioic acid, phosphorodiamidimidothioic acid, bis(phosphoramidimidodithioic acid), bis(phosphorodiamidimidothioic acid), poly(phospboramidimidodithioic acid), poly(phosphorodiamidimidothioic acid), and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoramidimidodithioic acid, phosphorodiamidimidothioic acid, S-phenylphosphoramidimidodithioic acid; S-benzylphosphoramidimidodithoic acid; S-naphthylphosphoramidimidodithioic acid; S-cyclohexylphosphoramidimidodithioic acid; S-norbornylphosphoramidimidodithioic acid; S,S′-diphenylphosphoramidimidodithioic acid; S,S′-dibenzylphosphoramidimidodithioic acid; S,S′-dinaphthylphosphoramidimidodithioic acid; S,S′-dicyclohexylphosphoramidimidodithioic acid; and S,S′-dinorbornylphosphoramidimidodithioic acid.

N Valence Stabilizer #31: Examples of azo compounds with amino, imino, oximo, diazeno, or hydrazido substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, bis[o-(H ₂N—) or alpha- or beta-(H₂N—)azo compounds], or poly[o-(H₂N—) or alpha- or beta-(H₂N—)azo compounds) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn⁺³and/or Mn⁺⁴include, but are not limited to: o-aminoazobenzene; o,o′-diaminoazobenzene; (2-pyridine)azobenzene; 1-phenylazo-2-naphthylamine; pyridineazo-2-naphthol (PAN); pyridineazoresorcinol (PAR); o-hydroxy-o′-(beta-aminoethylamino)azobenzene; Benzopurpurin 4B; Congo Red; Fat Brown RR; benzopurpurin; Congo Red; Direct Red 75; Mordant Brown 48; Nitro Red; 2-imidazolylazobenzene; 2-benzimidazolylazobenzene; 3-pyrazolylazobenzene; 3-(1,2,4-triazolyl)azobenzene; 2-pyridylazobenzene; 2-pyrazinylazobenzene; and 2-pyrimidinylazobenzene.

N Valence Stabilizer #32: Examples of diazeneformimidamides (diazeneamidines), diazeneacetimidamides (diazene-alpha-amidinoalkanes(alkenes)), bis(diazeneformimidamides), bis(diazeneacetimidamides), poly(diazeneformimidamides), and poly(diazeneacetimidamides) (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformimidamide (diazeneamidine); diazeneacetimidamide (diazene-alpha-amidinomethane); phenyldiazeneformimidamide; triphenyldiazeneformimidamide; phenyldiazeneacetimidamide; and triphenyldiazeneacetimidamide.

N Valence Stabilizer #33: Examples of diazeneformimidic acid, diazeneacetimidic acid, bis(diazeneformimidic acid), bis(diazeneacetimidic acid), poly(diazeneformimidic acid), poly(diazeneacetimidic acid), and derivatives thereof (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformimidic acid, diazeneacetimidic acid, phenyldiazeneformimidic acid, diphenyldiazeneformimidic acid, phenyldiazeneacetimidic acid, and diphenyldiazeneacetimidic acid.

N Valence Stabilizer #34: Examples of diazeneformimidothioic acid, diazeneacetimidothioic acid, bis(diazeneformimidothioic acid), bis(diazeneacetimidothioic acid), poly(diazeneformimidothioic acid), poly(diazeneacetimidothioic acid), and derivatives thereof (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformimidothioic acid, diazeneacetimidothioic acid, phenyldiazeneformimidothioic acid, diphenyldiazeneformimidothioic acid, phenyldiazeneacetimidothioic acid, and diphenyldiazeneacetimidothioic acid.

N Valence Stabilizer #35: Examples of imidoyldiazenes, bis(imidoyldiazenes), and poly(imidoyldiazenes), (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetimidoyldiazene; benzimidoyldiazene; and cyclohexylimidoyldiazene.

N Valence Stabilizer #36: Examples of diazenediformimidamides (1,2-diazenediamidines), diazenediacetimidamides (1,2-diazene-di-alpha-amidinoalkanes(alkenes)), bis(diazenediformimidamides), bis(diazenediacetimidamides), poly(diazenediformimidamides), and poly(diazenediacetimidamides) (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenediformimidamide (1,2-diazenediamidine), diazenediacetimidamide (1,2-diazene-di-alpha-amidinomethane); diphenyldiazenediformimidamide; tetraphenyldiazenediformimidamide; diphenyldiazenediacetimidamide; and tetraphenyldiazenediacetimidamide.

N Valence Stabilizer #37: Examples of diazenediformimidic acid, diazenediacetimidic acid, bis(diazenediformimidic acid), bis(diazenediacetimidic acid), poly(diazenediformimidic acid), and poly(diazenediacetimidic acid), and derivatives thereof (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenediformimidic acid, diazenediacetimidic acid, diphenyldiazenediformimidic acid, and diphenyldiazenediacetimidic acid.

N Valence Stabilizer #38: Examples of diazenediformimidothioic acid, diazenediacetimidothioic acid, bis(diazenediformimidothioic acid), bis(diazenediacetimidothioic acid), poly(diazenediformimidothioic acid), and poly(diazenediacetimidothioic acid), and derivatives thereof (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenediformimidothioic acid, diazenediacetimidothioic acid, diphenyldiazenediformimidothioic acid, and diphenyldiazenediacetimidothioic acid.

N Valence Stabilizer #39: Examples of diimidoyldiazenes, bis(diimidoyldiazenes), and poly(diimidoyldiazenes), (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diacetimidoyldiazene; dibenzimidoyldiazene; and dicyclohexylimidoyldiazene.

N Valence Stabilizer #40: Examples of ortho-amino (or -hydrazido) substituted formazans, bis(o-amino or -hydrazido substituted formazans), and poly(o-amino or -hydrazido substituted formazans) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1-(2-aminophenyl)-3,5-diphenylformazan; and 1,5-bis(2-aminophenyl)-3-phenylformazan.

N Valence Stabilizer #41: Examples of ortho-amino (or -hydrazido) substituted azines (including ketazines), bis(o-amino or hydrazido substituted azines), and poly(o-amino or hydrazido substituted azines) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-amino-1-benzalazine; 2-amino-1-naphthalazine; and 2-amino-1-cyclohexanonazine.

N Valence Stabilizer #42: Examples of Schiff Bases with one Imine (C═N) Group and with ortho- or alpha- or beta-amino or imino or oximo or diazeno or hydrazido substitution (N—N Bidentates, N—N Tridentates, N—N Tetradentates, N—N Pentadentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-(2-Aminobenzaldehydo)isopropylamine; N-(2-Pyridinecarboxaldehydo)isopropylamine; N-(2-Pyrrolecarboxaldehydo)isopropylamine; N-(2-Acetylpyridino)isopropylamine; N-(2-Acetylpyrrolo)isopropylamine; N-(2-Aminoacetophenono)isopropylamine; N-(2-Aminobenzaldehydo)cyclohexylamine; N-(2-Pyridinecarboxaldehydo)cyclohexylamine; N-(2-Pyrrolecarboxaldehydo)cyclohexylamine; N-(2-Acetylpyridino)cyclohexylamine; N-(2-Acetylpyrrolo)cyclohexylamine; N-(2-Aminoacetophenono)cyclohexylamine; N-(2-Aminobenzaldehydo)aniline; N-(2-Pyridinecarboxaldehydo)aniline; N-(2-Pyrrolecarboxaldehydo)aniline; N-(2-Acetylpyridino)aniline; N-(2-Acetylpyrrolo)aniline; N-(2-Aminoacetophenono)aniline; N-(2-Aminobenzaldehydo)aminonorbornane; N-(2-Pyridinecarboxaldehydo)aminonorbornane; N-(2-Pyrrolecarboxaldehydo)aminonorbornane; N-(2-Acetylpyridino)aminonorbornane; N-(2-Acetylpyrrolo)aminonorbornane; N-(2-Aminoacetophenono)aminonorbornane; 2-pyrrolecarboxaldehyde phenylhydrazone; 2-pyrrolecarboxaldehyde 2-pyridyl hydrazone; 2-aminobenzaldehyde phenylhydrazone (nitrin); and 2-aminobenzaldehyde 2-pyridyl hydrazone. Also includes hydrazones with ortho-N substitution.

N Valence Stabilizer #43: Examples of Schiff Bases with two Imine (C═N) Groups and without ortho- (for aryl constituents) or alpha- or beta- (for alkyl constituents) hydroxy, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido substitution (N—N Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-(Glyoxalo)diisopropylamine; N,N′-(Glyoxalo)dicyclohexylamine; N,N′-(Glyoxalo)dianiline; N,N′-(Glyoxalo)di-aminonorbornane; N,N′-(Malondialdehydo)diisopropylamine; N,N′-(Malondialdehydo)dicyclohexylamine; N,N′-(Malondialdehydo)dianiline; N,N′-(Malondialdehydo)di-aminonorbornane; N,N′-(Phthalicdialdehydo)diisopropylamine; N,N′-(Phthalicdialdehydo)dicyclohexylamine; N,N′-(Phthalicdialdehydo)dianiline; N,N′-(Phthalicdialdehydo)di-aminonorbornane; N,N′-(Formylcamphoro)diisopropylamine; N,N′-(Formylcamphoro)dicyclohexylamine; N,N′-(Formylcamphoro)dianiline; N,N′-(Formylcamphoro)di-aminonorbornane; N,N′-(Acetylacetonato)diisopropylamine; N,N′-(Acetylacetonato)dicyclohexylamine; N,N′-(Acetylacetonato)dianiline; N,N′-(Acetyl acetonato)di-aminonorbornane; N,N′-(Diacetylbenzeno)diisopropylamine; N,N′-(Diacetylbenzeno)dicyclohexylamine; N,N′-(Diacetylbenzeno)dianiline; N,N′-(Diacetylbenzeno)di-aminonorbornane; N,N′-(1,2-Cyclohexanono)diisopropylamine; N,N′-(1,2-Cyclohexanono)dicyclohexylamine; N,N′-(1,2-Cyclohexanono)dianiline; N,N′-(1,2-Cyclohexanono)di-aminonorbornane; N,N′-(Camphorquinono)diisopropylamine; N,N′-(Camphorquinono)dicyclohexylamine; N,N′-(Camphorquinono)dianiline; N,N′-(Camphorquinono)di-aminonorbornane; N,N′-(Benzaldehydo)ethylenediamine; N,N′-(Naphthaldehydo)ethylenediamine; N,N′-(Acetophenono)ethylenediamine; N,N′-(Benzaldehydo)trimethylenediamine; N,N′-(Naphthaldehydo)trimethylenediamine; N,N′-(Acetophenono)trimethylenediamine; N,N′-(Benzaldehydo)cyclohexane-1,2-diamine; N,N′-(Naphthaldehydo)cyclohexane-1,2-diamine; N,N′-(Acetophenono)cyclohexane-1,2-diamine; N,N′-(Benzaldehydo)-1,2-diaminobenzene; N,N′-(Naphthaldehydo)-1,2-diaminobenzene; N,N′-(Acetophenono)-1,2-diaminobenzene; N,N′-(Acetylacetonato)ethylenediamine; N,N′-(Acetylacetonato)-1,2-cyclohexylenediamine; N,N′-(Acetylacetonato)-1,2-propylenediamine; N,N′-(Glyoxalo)-o-phenylenediamine; and N,N′-(Glyoxalo)ethylenediamine. Also includes dihydrazones.

N Valence Stabilizer #44: Examples of Schiff Bases with two Imine (C═N) Groups and with ortho- or alpha- or beta-amino or imino or oximo or diazeno or hydrazido substitution (N—N Bidentates, N—N Tridentates, N—N Tetradentates, N—N Pentadentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-(2,6-Pyridinedicarboxaldehydo)diisopropylamine; N,N′-(2,6-Pyridinedicarboxaldehydo)dicyclohexylamine; N,N′-(2,6-Pyridinedicarboxaldehydo)dianiline; N,N′-(2,6-Pyridinedicarboxaldehydo)di-aminonorbornane; N,N′-(2,5-Pyrroledicarboxaldehydo)diisopropylamine; N,N′-(2,5-Pyrroledicarboxaldehydo)dicyclohexylamine; N,N′-(2,5-Pyrroledicarboxaldehydo)dianiline; N,N′-(2,5-Pyrroledicarboxaldehydo)di-aminonorbornane; N,N′-(o-Aminophthalicdialdehydo)diisopropylamine; N,N′-(o-Aminophthalicdialdehydo)dicyclohexylamine; N,N′-(o-Aminophthalicdialdehydo)dianiline; N,N′-(o-Aminophthalicdialdehydo)di-aminonorbornane; N,N′-(o-Aminoformylcamphoro)diisopropylamine; N,N′-(o-Aminoformylcamphoro)dicyclohexylamine; N,N′-(o-Aminoformylcamphoro)dianiline; N,N′-(o-Aminoformylcamphoro)di-aminonorbornane; N,N′-(2,6-Diacetylpyridino)diisopropylamine; N,N′-(2,6-Diacetylpyridino)dicyclohexylamine; N,N′-(2,6-Diacetylpyridino)dianiline; N,N′-(2,6-Diacetylpyridino)di-aminonorbornane; N,N′-(o-Aminodiacetylbenzeno)diisopropylamine; N,N′-(o-Aminodiacetylbenzeno)dicyclohexylamine; N,N′-(o-Aminodiacetylbenzeno)dianiline; N,N′-(o-Aminodiacetylbenzeno)di-aminonorbornane; N,N′-(3,6-Diamino-1,2-cyclohexanono)diisopropylamine; N,N′-(3,6-Diamino-1,2-cyclohexanono)dicyclohexylamine; N,N′-(3,6-Diamino-1,2-cyclohexanono)dianiline; N,N′-(3,6-Diamino-1,2-cyclohexanono)di-aminonorbornane; N,N′-(2,5-Diacetylpyrrolo)diisopropylamine; N,N′-(2,5-Diacetylpyrrolo)dicyclohexylamine; N,N′-(2,5-Diacetylpyrrolo)dianiline; N,N′-(2,5-Diacetylpyrrolo)di-aminonorbornane; N,N′-(o-Aminobenzaldehydo)ethylenediamine; N,N′-(o-Aminonaphthaldehydo)ethylenediamine; N,N′-(o-Aminoacetophenono)ethylenediamine; N,N′-(o-Aminobenzaldehydo)trimethylenediamine; N,N′-(o-Aminonaphthaldehydo)trimethylenediamine; N,N′-(o-Aminoacetophenono)trimethylenediamine; N,N′-(o-Aminobenzaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Aminonaphthaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Aminoacetophenono)cyclohexane-1,2-diamine; N,N′-(o-Aminobenzaldehydo)-1,2-diaminobenzene; N,N′-(o-Aminonaphthaldehydo)-1,2-diaminobenzene; and N,N′-(o-Aminoacetophenono)-1,2-diaminobenzene. Also includes hydrazones with ortho-N substitution.

N Valence Stabilizer #45: Examples of Schiff Bases with three Imine (C—N) Groups and without ortho- (for aryl constituents) or alpha- or beta- (for alkyl constituents) hydroxy, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido substitution (N—N Tridentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′,N″-(Benzaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(Naphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(Acetophenono)tris(2-aminoethyl)amine. Also includes trihydrazones.

N Valence Stabilizer #46: Examples of Schiff Bases with three Imine (C═N) Groups and with ortho- or alpha- or beta-amino or imino or oximo or diazeno or hydrazido substitution (N—N Tridentates, N—N Tetradentates, N—N Pentadentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′,N″-(o-Aminobenzaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(o-Aminonaphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(o-Aminoacetophenono)tris(2-aminoethyl)amine.

S Valence Stabilizer #1: Examples of macrocyclic, macrobicyclic, and macropolycyclic oligothioketones (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of thioketones (especially in the beta position) (S—S Bidentates, S—S Tetradentates, and S—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexathioketocyclotetracosane ([24]ane(═S)₆); hexathioketocycloheneicosane ([21]ane(═S)₆); hexathioketocyclooctadecane ([18]ane(═S)₆); hexathioketocyclopentadecane ([15]ane(S)₆); tetrathioketocycloeicosane ([20]ane(═S)₄); tetrathioketocyclooctadecane ([18]ane(═S)₄); tetrathioketocyclohexadecane ([16]ane(═S)₄); tetrathioketocyclotetradecane ([14]ane(S)₄); tetrathioketocyclododecane ([12]ane(═S)₄); dithioketocyclohexadecane ([16]ane(═S)₂); dithioketocyclotetraadecane ([14]ane(═S)₂); dithioketocyclododecane ([12]ane(═S)₂); dithioketocyclodecane ([1]ane(S)₂); and dithioketocyclooctane ([8]ane(═S)₂).

S Valence Stabilizer #2: Examples of macrocyclic, macrobicyclic, and macropolycyclic dithiolenes (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of alpha-, alpha-dithiolenes (meaning two thiol groups on a single carbon atom in the ring) (S—S Bidentates, S—S Tetradentates, and S—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexathiolocyclotetracosane ([24]ane(—SH)₆); hexathiolocycloheneicosane ([21]ane(—SH)₆); hexathiolocyclooctadecane ([18]ane(—SH)₆); hexathiolocyclopentadecane ([15]ane(—SH)₆); tetrathiolocycloeicosane ([20]ane(—SH)₄); tetrathiolocyclooctadecane ([18]ane(—SH)₄); tetrathiolocyclohexadecane ([16]ane(—SH)₄); tetrathiolocyclotetradecane ([14]ane(—SH)₄); tetrathiolocyclododecane ([12]ane(—SH)₄); dithiolocyclohexadecane ([16]ane(—SH)₂); dithiolocyclotetraadecane ([14]ane(—SH)₂); dithiolocyclododecane ([12]ane(—SH)₂); dithiolocyclodecane ([11]ane(—SH)₂); and dithiolocyclooctane ([8]ane(—SH)₂).

S Valence Stabilizer #3: Examples of dithioimidodialdehydes, dithiohydrazidodialdehydes (thioacyl thiohydrazides), bis(dithioimidodialdehydes), bis(dithiohydrazidodialdehydes), poly(ditbioimidodialdehydes), and poly(dithiohydrazidodialdehydes) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodiacetamide, dithiodipropanamide, dithiodibutanamide, dithiodibenzamide, and dithiodicyclohexamide.

S Valence Stabilizer #4: Examples of dithioimidodicarbonic acids, dithiohydrazidodicarbonic acids, bis(dithioimidodicarbonic acids), bis(dithiohydrazidodicarbonic acids), poly(dithioimidodicarbonic acids), poly(dithiohydrazidodicarbonic acids) and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioimidodicarbonic acid, dithiohydrazidodicarbonic acid, O-pbenyldithioimidodicarbonic acid, O-benzyldithioimidodicarbonic acid, O-cyclohexyldithioimidodicarbonic acid, O-norbornyldithioimidodicarbonic acid, O,O′-diphenyldithioimidodicarbonic acid, O,O′-dibenzyldithioimidodicarbonic acid, O,O′-dicyclohexyldithioimidodicarbonic acid, and O,O′-norbornyldithioimidodicarbonic acid.

S Valence Stabilizer #5: Examples of 1,3-dithioketones (dithio-beta-ketonates), 1,3,5-trithioketones, bis(1,3-dithioketones), and poly(1,3-dithioketones) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexafluoropentanedithione; 1,3-diphenyl-1,3-propanedithione; thiobenzoylthiopinacolone; dithiocyclohexoylmethane; diphenylpentanetrithionate; tetramethylnonanetrithionate; bexafluoroheptanetrithionate; trifluoroheptanetrithionate; 1-(2-thienyl)-1,3-butanedithione, 1-(2-naphthyl)-1,3-butanedithione, trifluorothioacetylthiocampbor; and 1,3-indandithione.

S Valence Stabilizer #6: Examples of 1,2-dithioketones (dithiolenes, dithio-alpha-ketonates), 1,2,3-trithioketones, dithiotropolonates, o-dithioquinones, bis(1,2-dithioketones), and poly(1,2-dithioketones) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiotropolone; 1,2-dithiobenzoquinone (o-dithioquinone)(o-benzenedithiolate)(bdt); di-tert-butyl-1,2-dithiobenzoquinone; hexafluoro-1,2-dithiobenzoquinone; 1,2-ditbionaphthoquinone; 9,10-dithiophenanthroquinone; ethylenedithiolene (edt); maleonitriledithiolene (mnt); trifluoromethyldithiolene (tfd); carbomethoxydithiolene (cmt); trithionedithiolene (dmit); toluenedithiolate (tdt); dithiomanaldehyde (propenethionethiolate)(ptt); dithioacetylacetonate (SacSac); dijulolidinedithiolene; 2,3-piperazinedithiolate; di(4-aminophenyl)dithiolene; dimercaptoisotrithione (dmit); (4-octylphenyl)dithiolene; benzenetetrathiol; tetrathiosquaric acid; trithiodeltic acid; pentathiocroconic acid; dithiocroconic acid; hexathiorhodizonic acid; dithiorhodizonic acid; ethylenetetrathiol; trans-butadienetetrathiolate; tetrathiooxalic acid; 1,2-indandithione; naphthothioquinone; acenapthenethioquinone; aceanthrenethioquinone; and indole-2,3-dithione (thioisatin).

S Valence Stabilizer #7: Examples of dithiomalonamides (dithiomalonodiamides), bis(dithiomalonamides), and polydithiomalonamides (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiomalonamide, N-phenyldithiomalonamide, N-benzyldithiomalonamide, N-pentafluorophenyldithiomalonamide, N-cyclohexyldithiomalonamide, N-norbornyldithiomalonamide, N,N′-diphenyldithiomalonamide, N,N′-dibenzyldithiomalonamide, N,N′-dipentafluorophenyldithiomalonamide, N,N′-dicyclohexyldithiomalonamide, and N,N′-norbornyldithiomalonamide.

S Valence Stabilizer #8: Examples of 2-thioacylthioacetamides, bis(2-thioacylthioacetamides), and poly(2-thioacylthioacetamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-thioacetothioacetamide, N-phenyl-2-thioacetothioacetamide, N-pentafluorophenyl-2-thioacetothioacetamide, N-benzyl-2-thioacetothioacetamide, N-cyclohexyl-2-thioacetothioacetamide, N-norbornyl-2-thioacetothioacetamide, N-phenyl-2-thiobenzothioacetamide, N-pentafluorophenyl-2-pentafluorothiobenzothioacetamide, and N-cyclohexyl-2-thiocyclohexothioacetamide.

S Valence Stabilizer #9: Examples of dithioacyl sulfides, bis(dithioacyl sulfides), and poly(dithioacyl sulfides), (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioacetyl sulfide; dithiopropanoyl sulfide; dithiobenzoyl sulfide; and dithiopentafluorobenzoyl sulfide.

S Valence Stabilizer #10: Examples of trithiodicarbonic diamides, bis(trithiodicarbonic diamides), and poly(trithiodicarbonic diamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithiodicarbonic diamide; N-phenyltrithiodicarbonic diamide; N-pentafluorophenyltrithiodicarbonic diamide; N-benzyltrithiodicarbonic diamide; N-cyclohexyltrithiodicarbonic diamide; N-norbornyltrithiodicarbonic diamide; N,N′-diphenyltrithiodicarbonic diamide; N,N′-dipentafluorophenyltrithiodicarbonic diamide; N,N′-dibenzyltrithiodicarbonic diamide; N,N′-dicyclohexyltrithiodicarbonic diamide; and N,N′-dinorbornyltrithiodicarbonic diamide.

S Valence Stabilizer #11: Examples of pentathio-, tetrathio-, or trithiodicarbonic acids, bis(pentathio-, tetrathio-, or trithiodicarbonic acids), poly(pentathio-, tetrathio-, or trithiodicarbonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pentathiodicarbonic acid, tetrathiodicarbonic acid, trithiodicarbonic acid, O-phenyltrithiodicarbonic acid, O-benzyltrithiodicarbonic acid, O-cyclohexyltrithiodicarbonic acid, O-norbornyltrithiodicarbonic acid, O,O′-diphenyltrithiodicarbonic acid, O,O′-dibenzyltrithiodicarbonic acid, O,O′-dicyclohexyltrithiodicarbonic acid, and O,O′-dinorbornyltrithiodicarbonic acid.

S Valence Stabilizer #12: Examples of dithiohypophosphoric acids, bis(dithiohypophosphoric acids), poly(dithiohypophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiohypophosphoric acid, methyldithiohypophosphoric acid, isopropyldithiohypophosphoric acid, tert-butyldithiohypophosphoric acid, phenyldithiohypophosphoric acid, pentafluorophenyldithiohypophosphoric acid, benzyldithiohypophosphoric acid, cyclohexyldithiohypophosphoric acid, norbornyldithiohypophosphoric acid, dimethyldithiohypophosphoric acid, diisopropyldiothiohypophosphoric acid, di-tert-butyldithiohypophosphoric acid, diphenyldithiohypophosphoric acid, dipentafluorophenyldithiohypophosphoric acid, dibenzyldithiohypophosphoric acid, dicyclohexyldithiohypophosphoric acid, and dinorbornyldithiohypophosphoric acid.

S Valence Stabilizer #13: Examples of dithiohypophosphoramides, bis(dithiohypophosphoramides), and poly(dithiohypophosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiohypophosphoramide, N-methyldithiohypophosphoramide, N-isopropyldithiohypophosphoramide, N-tert-butyldithiohypophosphoramide, N-phenyldithiohypophosphoramide, N-pentafluorophenyldithiohypophosphoramide, N-benzyldithiohypophosphoramide, N-cyclohexyldithiohypophosphoramide, N-norbornyldithiohypophosphoramide, N,N′″-dimethyldithiohypophosphoramide, N,N′″-diisopropyldithiohypophosphoramide, N,N′″-di-tert-butyldithiohypophosphoramide, N,N′″-diphenyldithiohypophosphoramide, N,N′″-di-pentafluorophenyldithiohypophosphoramide, N,N′″-dibenzyldithiohypophosphoramide, N,N′″-dicyclohexyldithiohypophosphoramide, and N,N′″-dinorbornyldithiohypophosphoramide.

S Valence Stabilizer #14: Examples of dithioimidodiphosphoric acids, dithiohydrazidodiphosphoric acids, bis(dithioimidodiphosphoric acids), bis(dithiohydrazidodiphosphoric acids), poly(dithioimidodiphosphoric acids), poly(dithiohydrazidodiphosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioimidodiphosphoric acid, methyldithioimidodiphosphoric acid, isopropyldithioimidodiphosphoric acid, tert-butyldithioimidodiphosphoric acid, phenyldithioimidodiphosphoric acid, pentafluorophenyldithioimidodiphosphoric acid, benzyldithioimidodiphosphoric acid, cyclohexyldithioimidodiphosphoric acid, norbornyldithioimidodiphosphoric acid, dimethyldithioimidodiphosphoric acid, diisopropyldiothioimidodiphosphoric acid, di-tert-butyldithioimidodiphosphoric acid, diphenyldithioimidodiphosphoric acid, di-pentafluorophenyldithioimidodiphosphoric acid, dibenzyldithioimidodiphosphoric acid, dicyclohexyldithioimidodiphosphoric acid, and dinorbornyldithioimidodiphosphoric acid.

S Valence Stabilizer #15: Examples of dithioimidodiphosphoramides, dithiohydrazidodiphosphoramides, bis(dithioimidodiphosphoramides), bis(dithiohydrazidodiphosphoramides), poly(dithioimidodiphosphoramides), and poly(dithiohydrazidodiphosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioimidodiphosphoramide, N-methyldithioimidodiphosphoramide, N-isopropyldithioimidodiphosphoramide, N-tert-butyldithioimidodiphosphoramide, N-phenyldithioimidodiphosphoramide, N-pentafluorophenyldithioimidodiphosphoramide, N-benzyldithioimidodiphosphoramide, N-cyclohexyldithioimidodiphosphoramide, N-norbornyldithioimidodiphosphoramide, N,N′″-dimethyldithioimidodiphosphoramide, N,N′″-diisopropyldithioimidodiphosphoramide, N,N′″-di-tert-butyldithioimidodiphosphoramide, N,N′″-diphenyldithioimidodiphosphoramide, N,N′″-di-pentafluorophenyldithioimidodiphosphoramide, N,N′″-dibenzyldithioimidodiphosphoramide, N,N′″-dicyclohexyldithioimidodiphosphoramide, and N,N′″-dinorbornyldithioimidodiphosphoramide.

S Valence Stabilizer #16: Examples of dithiodiphosphoramides, bis(dithiodiphosphoramides), and poly(dithiodiphosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodiphosphoramide, N-methyldithiodiphosphoramide, N-isopropyldithiodiphosphoramide, N-tert-butyldithiodiphosphoramide, N-phenyldithiodiphosphoramide, N-pentafluorophenyldithiodiphosphoramide, N-benzyldithiodiphosphoramide, N-cyclohexyldithiodiphosphoramide, N-norbornyldithiodiphosphoramide, N,N′″-dimethyldithiodiphosphoramide, N,N′″-diisopropyldithiodiphosphoramide, N,N′″-di-tert-butyldithiodiphosphoramide, N,N′″-diphenyldithiodiphosphoramide, N,N′″-di-pentafluorophenyldithiodiphosphoramide, N,N′″-dibenzyldithiodiphospboramide, N,N′″-dicyclohexyldithiodiphosphoramide, and N,N′″-dinorbornyldithiodiphosphoramide.

S Valence Stabilizer #17: Examples of dithiodiphosphoric acids, bis(dithiodiphosphoric acids), poly(dithiodiphosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodiphosphoric acid, methyldithiodiphosphoric acid, isopropyldithiodiphosphoric acid, tert-butyldithiodiphosphoric acid, phenyldithiodiphosphoric acid, pentafluorophenyldithiodiphosphoric acid, benzyldithiodiphosphoric acid, cyclohexyldithiodiphosphoric acid, norbornyldithiodiphosphoric acid, dimethyldithiodiphosphoric acid, diisopropyldiothiodiphosphoric acid, di-tert-butyldithiodiphosphoric acid, diphenyldithiodiphosphoric acid, di-pentafluorophenyldithiodiphosphoric acid, dibenzyldithiodiphosphoric acid, dicyclohexyldithiodiphosphoric acid, and dinorbornyldithiodiphosphoric acid.

S Valence Stabilizer #18: Examples of trithiophosphoric acids (phosphorotritbioic acids), bis(trithiophosphoric acids), poly(trithiophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithiophosphoric acid, O-phenyltrithiophosphoric acid, O-benzyltrithiophosphoric acid, O-cyclohexyltrithiophosphoric acid, O-norbornyltrithiophosphoric acid, O,S-diphenyltrithiophosphoric acid, O,S-dibenzyltrithiophosphoric acid, O,S-dicyclohexyltrithiophosphoric acid, and O,S-dinorbornyltrithiophosphoric acid.

S Valence Stabilizer #19: Examples of dithiophosphoric acids (phosphorodithioic acids), bis(dithiophosphoric acids), poly(dithiophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiophosphoric acid, O-phenyldithiophosphoric acid, O-benzyldithiophosphoric acid, O-cyclohexyldithiophosphoric acid, O-norbornyldithiophosphoric acid, O,O-diphenyldithiophosphoric acid, O,O-dibenzyldithiophosphoric acid, O,O-dicyclohexyldithiophosphoric acid, and O,O-dinorbornyldithiophosphoric acid.

S Valence Stabilizer #20: Examples of tetrathiophosphoric acids (phosphorotetrathioic acids), bis(tetrathiophosphoric acids), poly(tetrathiophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrathiophosphoric acid, S-phenyltetrathiophosphoric acid, S-benzyltetrathiophosphoric acid, S-cyclohexyltetrathiophosphoric acid, S-norbornyltetrathiophosphoric acid, S,S-diphenyltetrathiophosphoric acid, S,S-dibenzyltetrathiophosphoric acid, S,S-dicyclohexyltetrathiophosphoric acid, and S,S-dinorbornyltetrathiophosphoric acid.

S Valence Stabilizer #21: Examples of phosphoro(dithioperoxo)dithioic acids, bis[phosphoro(dithioperoxo)dithioic acids], poly[phosphoro(dithioperoxo)dithioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: phosphoro(dithioperoxo)dithioic acid, O-phenylphosphoro(dithioperoxo)dithioic acid, O-benzylphosphoro(dithioperoxo)dithioic acid, O-cyclohexylphosphoro(dithioperoxo)dithioic acid, O-norbornylphosphoro(dithioperoxo)dithioic acid, O,S-diphenylphosphoro(dithioperoxo)dithioic acid, O,S-dibenzylphosphoro(dithioperoxo)ditbioic acid, O,S-dicyclohexylphosphoro(dithioperoxo)dithioic acid, and O,S-dinorbornylphosphoro(dithioperoxo)dithioic acid.

S Valence Stabilizer #22: Examples of phosphoro(dithioperoxo)thioic acids, bis[phosphoro(dithioperoxo)thioic acids], poly[phosphoro(dithioperoxo)thioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoro(dithioperoxo)thioic acid, O-phenylphosphoro(dithioperoxo)thioic acid, O-benzylphosphoro(dithioperoxo)thioic acid, O-cyclohexylphosphoro(dithioperoxo)thioic acid, O-norbornylphosphoro(ditbioperoxo)thioic acid, O,S-diphenylphosphoro(dithioperoxo)thioic acid, O,S-dibenzylphosphoro(dithioperoxo)thioic acid, O,S-dicyclohexylphosphoro(dithioperoxo)thioic acid, and O,S-dinorbornylphosphoro(dithioperoxo)thioic acid.

S Valence Stabilizer #23: Examples of phosphoro(dithioperoxo)trithioic acids, bis[phosphoro(dithioperoxo)trithioic acids], poly[phosphoro(dithioperoxo)trithioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoro(dithioperoxo)trithioic acid, O-phenylphosphoro(dithioperoxo)trithioic acid, O-benzylphosphoro(dithioperoxo)trithioic acid, O-cyclohexylphosphoro(dithioperoxo)trithioic acid, O-norbornylphosphoro(dithioperoxo)trithioic acid, O,S-diphenylphosphoro(dithioperoxo)trithioic acid, O,S-dibenzylphosphoro(dithioperoxo)trithioic acid, O,S-dicyclohexylphosphoro(dithioperoxo)trithioic acid, and O,S-dinorbornylphosphoro(dithioperoxo)trithioic acid.

S Valence Stabilizer #24: Examples of beta-mercaptothioketones, beta-mercaptothioaldehydes, bis(beta-mercaptothioketones), bis(beta-mercaptothioaldehydes), poly(beta-mercaptothioketones), and poly(beta-mercaptothioaldehydes) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-mercaptopentan-2-thione; 1,3-diphenyl-3-mercaptopropanethioaldehyde; 1,3-dibenzyl-3-mercaptopropanethioaldehyde; 1,3-dicyclohexyl-3-mercaptopropanethioaldehyde; 1,3-dinorbornyl-3-mercaptopropanethioaldehyde; 1,3-di(2-thienyl)-3-mercaptopropanethioaldehyde; 1,3-di(2-furyl)-3-mercaptopropanethioaldehyde; o-mercaptothioacetophenone; 5-mercapto-1,4-dithionaphthoquinone; 1-mercaptothioacridone; 1-mercaptodithioanthraquinone; 1,8-dimercaptodithioanthraquinone; and beta-mercaptothiobenzophenone.

S Valence Stabilizer #25: Examples of N-(aminomethylthiol)thioureas [N-(aminomercaptomethyl)thioureas], bis[N-(aminomethylthiol)thioureas], and poly[N-(aminomethylthiol)thioureas] (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N′-(aminomercaptomethyl)thiourea; N,N″-dimethyl-N′-(aminomercaptomethyl)thiourea; N,N′-diethyl-N′-(aminomercaptomethyl)thiourea; N,N″-isopropyl-N′-(aminomercaptomethyl)thiourea; N,N″-diphenyl-N′-(aminomercaptomethyl)thiourea; N,N″-dibenzyl-N′-(aminonercaptomethyl)thiourea; N,N″-dicyclohexyl-N′-(aminomercaptomethyl)thiourea; and N,N″-dinorbornyl-N′-(aminomercaptomethyl)thiourea.

S Valence Stabilizer #26: Examples of dithiooxamides, bis(dithiooxamides), and poly(dithiooxamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiooxamide (rubeanic acid), N-methyldithiooxamide; N-ethyldithiooxamide; N-isopropyldithiooxamide; N-phenyldithiooxamide; N-benzyldithiooxamide; N-cyclohexyldithiooxamide; N-norbornyldithiooxamide; N,N′-dimethyldithiooxamide; N,N′-diethyldithiooxamide; N,N′-diisopropyldithiooxamide; N,N′-diphenylditbiooxamide; N,N′-dibenzyldithiooxamide; N,N′-dicyclohexyldithiooxamide; and N,N′-dinorbornyldithiooxamide.

S Valence Stabilizer #27: Examples of 1,1-dithiolates, bis(1,1-dithiolates), and poly(1,1-dithiolates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,1-dicyano-2,2-ethylene dithiolate (i-mnt); 1,1-dicarboalkoxy-2,2-ethylene dithiolate (DED); 1,1-di(trifluoromethyl)-2,2-ethylenedithiolate; 1,1-di(pentafluorophenyl)-2,2-ethylenedithiolate; 1-pentamethylene-2,2-ethylene dithiolate; and 1-nitroethylene dithiolate.

S Valence Stabilizer #28: Examples of dithiomonocarboxylic acids, tri- and tetrathiodicarboxylic Acids, bis(dithiomonocarboxylic acids), bis(tri- and tetrathiodicarboxylic acids), poly(dithiomonocarboxylic acids), poly(tri- and tetrathiodicarboxylic acids), and derivatives thereof (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioacetic acid; dithiopropionic acid; dithiobenzoic acid (dtb); dithiophenylacetic acid (dtpa); dithiocyclohexanoic acid; dithiofuroic acid; dithionaphthoic acid; phenyl dithioacetate; phenyl dithiopropionate; phenyl dithiobenzoate; phenyl dithiocyclohexanoate; phenyl dithiofuroate; phenyl dithionaphthoate; tetrathiooxalic acid; tetrathiomalonic acid; tetrathiosuccinic acid; trithiooxalic acid; trithiomalonic acid; trithiosuccinic acid; diphenyl tetrathiooxalate; diphenyl tetrathiomalonate; diphenyl tetrathiosuccinate; diphenyl trithiooxalate; diphenyl trithiomalonate; diphenyl trithiosuccinate; pyridine dithiocarboxylic acid; pyrrole dithiocarboxylic acid; thiophene dithiocarboxylic acid; dithionaphthoic acid; and tetrathiocamphonic acid.

S Valence Stabilizer #29: Examples of perthiomonocarboxylic acids, perthiodicarboxylic acids, bis(perthiomonocarboxylic acids), bis(perthiodicarboxylic acids), poly(perthiomonocarboxylic acids), poly(perthiodicarboxylic acids), and derivatives thereof (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: perthioacetic acid; perthiopropionic acid; perthiobenzoic acid; perthiophenylacetic acid; perthiocyclohexanoic acid; perthiofuroic acid; perthionaphthoic acid; phenyl perthioacetate; phenyl perthiopropionate; phenyl perthiobenzoate; phenyl perthiocyclohexanoate; phenyl perthiofuroate; phenyl perthionaphthoate; perthiooxalic acid; perthiomalonic acid; perthiosuccinic acid; diphenyl perthiooxalate; diphenyl perthiomalonate; diphenyl perthiosuccinate; dithiole-3-thione (dithione-3-thione); and benzodithiole-3-thione (benzodithione-3-thione).

S Valence Stabilizer #30: Examples of dithiocarbonates, trithiocarbonates, perthiocarbonates, bis(dithiocarbonates), bis(trithiocarbonates), and bis(perthiocarbonates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: S,S-diethyldithiocarbonate; S,S-diisopropyldithiocarbonate; S,S-diphenyldithiocarbonate; S,S-dibenzyldithiocarbonate; S,S-dicyclohexyldithiocarbonate; S,S-dinorbornyldithiocarbonate; diethyltrithiocarbonate; diisopropyltrithiocarbonate; diphenyltrithiocarbonate; dibenzyltrithiocarbonate; dicyclohexyltrithiocarbonate; and dinorbornyltrithiocarbonate.

S Valence Stabilizer #31: Examples of dithiocarbamates, bis(dithiocarbamates), and poly(dithiocarbamates) (including N-hydroxydithiocarbamates and N-mercaptodithiocarbamates) (S—S Bidentates, S—S Tridentates, and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dimethyldithiocarbamate (dmdtc); di(trifluorodimethyl)dithiocarbamate; diethyldithiocarbamate (dedtc); dipropyldithiocarbamate; diisopropyldithiocarbamate; dibutyldithiocarbamate; ditertbutyldithiocarbamate; dicyanamidodithiocarbamate; azidothioformates; diphenyldithiocarbamate; di(pentafluorophenyl)dithiocarbamate; dibenzyldithiocarbamate; dinaphthyldithiocarbamate; dicyclohexyldithiocarbamate; dinorbornyldithiocarbamate; diadamantyldithiocarbamate; pyrrolidinodithiocarbamate (pyrdtc); piperidinodithiocarbamate (pipdtc); morpholinodithiocarbamate (mordtc); thiamorpholinodithiocarbamate; 3-pyrrolinodithiocarbamate; pyrrolodithiocarbamate; oxazolodithiocarbamate; isoxazolodithiocarbamate; thiazolodithiocarbamate; isothiazolodithiocarbamate; indolodithiocarbamate; carbazolodithiocarbamate; pyrazolinodithiocarbamate; imidazolinodithiocarbamate; pyrazolodithiocarbamate; imidazolodithiocarbamate; indazolodithiocarbamate; and triazolodithiocarbamate.

S Valence Stabilizer #32: Examples of dithiocarbazates (dithiocarbazides), bis(dithiocarbazates), and poly(dithiocarbazates) (S—S Bidentates, S—S Tridentates, and S—S Tetradentates; or possibly N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-dimethyldithiocarbazate; N,N′-di(trifluoromethyl)dithiocarbazate; N,N′-diethyldithiocarbazate; N,N′-diphenyldithiocarbazate; N,N′-dibenzyldithiocarbazate; N,N′-di(pentafluorophenyl)dithiocarbazate; N,N′-dicyclohexyldithiocarbazate; and N,N′-dinorbornyldithiocarbazate.

S Valence Stabilizer #33: Examples of thiocyanate ligands (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn include, but are not limited to: thiocyanate (—SCN).

O Valence Stabilizer #1: Examples of biurets (imidodicarbonic diamides), isobiurets, biureas, triurets, triureas, bis(biurets), bis(isobiurets), bis(biureas), poly(biurets), poly(isobiurets), and poly(biureas) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: biuret, isobiuret, biurea, triuret, triurea, nitrobiuret, dinitrobiuret, aminobiuret, diaminobiuret, oxybiuret, dioxybiuret, cyanobiuret, methylbiuret, ethylbiuret, isopropylbiuret, phenylbiuret, benzylbiuret, cyclohexylbiuret, norbornylbiuret, adamantylbiuret, dimethylbiuret, diethylbiuret, diisopropylbiuret, diphenylbiuret, dibenzylbiuret, dicyclohexylbiuret, dinorbornylbiuret, and diadamantylbiuret.

O Valence Stabilizer #2: Examples of acylureas, aroylureas, bis(acylureas), bis(aroylureas), poly(acylureas), and poly(aroylureas) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: formylurea, acetylurea, benzoylurea, cyclohexoylurea, pentafluorobenzoylurea, N-methylacetylurea, N-phenylbenzoylurea, and N-cyclohexylcyclohexoylurea.

O Valence Stabilizer #3: Examples of imidodialdehydes, hydrazidodialdehydes (acyl hydrazides), bis(imidodialdehydes), bis(hydrazidodialdehydes), poly(imidodialdehydes), and poly(hydrazidodialdehydes) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diacetamide, dipropanamide, dibutanamide, dibenzamide, and dicyclohexamide.

O Valence Stabilizer #4: Examples of imidodicarbonic acids, hydrazidodicarbonic acids, bis(imidodicarbonic acids), bis(hydrazidodicarbonic acids), poly(imidodicarbonic acids), poly(hydrazidodicarbonic acids) and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: imidodicarbonic acid, hydrazidodicarbonic acid, O-phenylimidodicarbonic acid, O-benzylimidodicarbonic acid, O-cyclohexylimidodicarbonic acid, o-norbornylimidodicarbonic acid, O,O′-diphenylimidodicarbonic acid, O,O′-dibenzylimidodicarbonic acid, O,O′-dicyclohexylimidodicarbonic acid, and O,O′-dinorbornylimidodicarbonic acid.

O Valence Stabilizer #5: Examples of imidodisulfamic acid, imidodisulfuric acid, bis(imidodisulfamic acid), bis(imidodisulfuric acid), poly(imidodisulfamic acid), and poly(imidodisulfuric acid) and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: imidodisulfamic acid, imidodisulfuric acid, N-phenylimidodisulfamic acid, N-benzylimidodisulfamic acid, N-cyclohexylimidodisulfamic acid, N-norbornylimidodisulfamic acid, N,N′-diphenylimidodisulfamic acid, N,N′-dibenzylimidodisulfainic acid, N,N′-dicyclohexylimidodisulfamic acid, and N,N′-norbornylimidodisulfamic acid.

O Valence Stabilizer #6: Examples of 1,3-diketones (beta-diketonates), 1,3,5-triketones, bis(1,3-diketones), and poly(1,3-diketones), all with a molecular weight greater than 125 (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexafluoropentanedione; dibenzoylmethane (1,3-diphenyl-1,3-propanedione); benzoylpinacolone; dicyclohexoylmethane; diphenylpentanetrionate; dibenzoylacetone; benzoylacetylacetone; dibenzoylacetylacetone; tetramethylnonanetrionate; hexafluoroheptanetrionate; trifluoroheptanetrionate; trifluoroacetylcamphor (facam); and 1,3-indandione.

O Valence Stabilizer #7: Examples of 1,2-diketones (alpha-diketonates), 1,2,3-triketones, tropolonates, o-quinones, bis(1,2-diketones), and poly(1,2-diketones), all with a molecular weight greater than 100 (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tropolone; 1,2-benzoquinone (o-quinone); di-tert-butyl-1,2-benzoquinone; hexafluoro-1,2-benzoquinone; 1,2-naphthoquinone; 9,10-phenanthroquinone; and 1,2-indandione.

O Valence Stabilizer #8: Examples of malonamides (malonodiamides), bis(malonamides), and polymalonamides (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: malonamide, N-phenylmalonamide, N-benzylmalonamide, N-pentafluorophenylmalonamide, N-cyclohexylmalonamide, N-norbornylmalonamide, N,N′-diphenylmalonainide, N,N′-dibenzylnalonamide, N,N′-dipentafluorophenylmalonamide, N,N′-dicyclohexylmalonamide, and N,N′-norbornylmalonamide.

O Valence Stabilizer #9: Examples of 2-acylacetamides, bis(2-acylacetamides), and poly(2-acylacetamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-acetoacetamide, N-phenyl-2-acetoacetamide, N-pentafluorophenyl-2-acetoacetamide, N-benzyl-2-acetoacetamide, N-cyclohexyl-2-acetoacetamide, N-norbornyl-2-acetoacetamide, N-phenyl-2-benzoacetamide, N-pentafluorophenyl-2-pentafluorobenzoacetamide, and N-cyclohexyl-2-cyclohexoacetamide.

O Valence Stabilizer #10: Examples of monothiodicarbonic diamides, bis(monothiodicarbonic diamides), and poly(monothiodicarbonic diamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiodicarbonic diamide; N-phenylmonothiodicarbonic diamide; N-pentafluorophenylmonothiodicarbonic diamide; N-benzylmonothiodicarbonic diamide; N-cyclohexylmonothiodicarbonic diamide; N-norbornylmonothiodicarbonic diamide; N,N′-diphenylmonothiodicarbonic diamide; N,N′-dipentafluorophenylmonothiodicarbonic diamide; N,N′-dibenzylmonothiodicarbonic diamide; N,N′-dicyclohexylmonothiodicarbonic diamide; and N,N′-dinorbornylmonothiodicarbonic diamide.

O Valence Stabilizer #11: Examples of monothiodicarbonic acids, bis(monothiodicarbonic acids), poly(monothiodicarbonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiodicarbonic acid, O-phenylmonothiodicarbonic acid, O-benzylmonothiodicarbonic acid, O-cyclohexylmonothiodicarbonic acid, O-norbornylmonothiodicarbonic acid, O,O′-diphenylmonothiodicarbonic acid, O,O′-dibenzylmonothiodicarbonic acid, O,O′-dicyclohexylmonothiodicarbonic acid, and O,O′-dinorbornylmonothiodicarbonic acid.

O Valence Stabilizer #12: Examples of trithionic acid, bis(trithionic acid), poly(trithionic acid), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphenyl trithionate, dipentafluorodiphenyl trithionate, dicyclohexyl trithionate, and dinorbornyl trithionate.

O Valence Stabilizer #13: Examples of hypophosphoric acids, bis(hypophosphoric acids), and poly(hypophosphoric acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hypophosphoric acid, O-methylhypophosphoric acid, O-isopropylhypophosphoric acid, O-tert-butylhypophosphoric acid, O-phenylhypophosphoric acid, O-pentafluorophenylhypophosphoric acid, O-benzylhypophosphoric acid, O-cyclohexylhypophosphoric acid, O-norbornylhypophosphoric acid, O,O″-dimethylhypophosphoric acid, O,O″-diisopropylhypophosphoric acid, O,O″-di-tert-butylhypophosphoric acid, O,O″-diphenylhypophosphoric acid, O,O″-di-pentafluorophenylhypophosphoric acid, O,O″-dibenzylhypophosphoric acid, O,O″-dicyclohexylhypophosphoric acid, and O,O″-dinorbornylhypophosphoric acid.

O Valence Stabilizer #14: Examples of hypophosphoramides, bis(hypophosphoramides), and poly(hypophosphoramides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hypophosphoramide, N-methylhypophosphoramide, N-isopropylhypophosphoramide, N-tert-butylhypophosphoramide, N-phenylhypophosphoramide, N-pentafluorophenylhypophosphoramide, N-benzylhypophosphoramide, N-cyclohexylhypophosphoramide, N-norbornylhypophosphoramide, N,N′″-dimethylhypophosphoramide, N,N′″-diisopropylhypophosphoramide, N,N′″-di-tert-butylhypophosphoramide, N,N′″-diphenylhypophosphoramide, N,N′″-di-pentafluorophenylhypophosphoramide, N,N′″-dibenzylhypophosphoramide, N,N′″-dicyclohexylhypophosphoramide, and N,N′″-dinorbornylhypophosphoramide.

O Valence Stabilizer #15: Examples of imidodiphosphoric acids, hydrazidodiphosphoric acids, bis(imidodiphosphoric acids), bis(hydrazidodiphosphoric acids), poly(imidodiphosphoric acids), poly(hydrazidodiphosphoric acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: imidodiphosphoric acid, methylimidodiphosphoric acid, isopropylimidodiphosphoric acid, tert-butylimidodiphosphoric acid, phenylimidodiphosphoric acid, pentafluorophenylimidodiphosphoric acid, benzylimidodiphosphoric acid, cyclohexylimidodiphosphoric acid, norbornylimidodiphosphoric acid, dimethylimidodiphosphoric acid, diisopropylimidodiphosphoric acid, di-tert-butylimidodiphosphoric acid, diphenylimidodiphosphoric acid, di-pentafluorophenylimidodiphosphoric acid, dibenzylimidodiphosphoric acid, dicyclohexylimidodiphosphoric acid, and dinorbornylimidodiphosphoric acid.

O Valence Stabilizer #16: Examples of imidodiphosphoramides, hydrazidodiphosphoramides, bis(imidodiphosphoramides), bis(hydrazidodiphosphoramides), poly(imidodiphosphoramides), and poly(hydrazidodiphosphoramides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: imidodiphosphoramide, N-methylimidodiphosphoramide, N-isopropylimidodiphosphoramide, N-tert-butylimidodiphosphoramide, N-phenylimidodiphosphoramide, N-pentafluorophenylimidodiphosphoramide, N-benzylimidodiphosphoramide, N-cyclohexylimidodiphosphoramide, N-norbornylimidodiphosphoramide, N,N′″-dimethylimidodiphosphoramide, N,N′″-diisopropylimidodiphosphoramide, N,N′″-di-tert-butylimidodiphosphoramide, N,N′″-diphenylimidodiphosphoramide, N,N′″-di-pentafluorophenylimidodiphosphoramide, N,N′″-dibenzylimidodiphosphoramide, N,N′″-dicyclohexylimidodiphosphoramide, and N,N′″-dinorbornylimidodipbosphoramide.

O Valence Stabilizer #17: Examples of diphosphoramides, bis(diphosphoramides), and poly(diphospboramides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphoramide, N-methyldphosphoramide, N-isopropyldiphosphoramide, N-tert-butyldiphosphoramide, N-phenyldiphosphoramide, N-pentafluorophenyldiphosphoramide, N-benzyldiphosphoramide, N-cyclohexyldiphosphoramide, N-norbornyldiphosphoramide, N,N′″-dimethyldiphosphoramide, N,N′″-diisopropyldiphosphoramide, N,N′″-di-tert-butyldiphosphoramide, N,N′″-diphenyldiphosphoramide, N,N′″-di-pentafluorophenyldiphosphoramide, N,N′″-dibenzyldiphosphoramide, N,N′″-dicyclohexyldiphosphoramide, and N,N′″-dinorbornyldiphosphoramide.

O Valence Stabilizer #18: Examples of beta-hydroxyketones, beta-hydroxyaldehydes, bis(beta-hydroxyketones), bis(beta-hydroxyaldehydes), poly(beta-hydroxyketones), and poly(beta-hydroxyaldehydes) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: 4-hydroxypentan-2-one; 1,3-diphenyl-3-hydroxypropanal; 1,3-dibenzyl-3-hydroxypropanal; 1,3-dicyclohexyl-3-hydroxypropanal; 1,3-dinorbornyl-3-hydroxypropanal; 1,3-di(2-thienyl)-3-hydroxypropanal; 1,3-di(2-furyl)-3-hydroxypropanal; o-hydroxyacetophenone; juglone; alizarin; 1-hydroxyanthraquinone; 1,8-hydroxyanthraquinone; 1-hydroxyacridone; and beta-hydroxybenzophenone.

O Valence Stabilizer #19: Examples of N-(aminomethylol)ureas [N-(aminohydroxymethyl)ureas], bis[N-(aminomethylol)ureas], and poly[N-(aminomethylol)ureas] (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N′-(aminohydroxymethyl)urea; N,N″-dimethyl-N′-(aminohydroxymethyl)urea; N,N′-diethyl-N′-(aminohydroxymethyl)urea; N,N″-isopropyl-N′-(aminohydroxymethyl)urea; N,N″-diphenyl-N′-(aminohydroxymethyl)urea; N,N″-dibenzyl-N′-(aminohydroxymethyl)urea; N,N″-dicyclohexyl-N′-(aminohydroxymethyl)urea; and N,N″-dinorbornyl-N′-(aminohydroxymethyl)urea.

O Valence Stabilizer #20: Examples of oxamides, bis(oxamides), and poly(oxamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: oxamide, N-methyloxamide; N-ethyloxamide; N-isopropyloxamide; N-phenyloxamide; N-benzyloxamide; N-cyclohexyloxamide; N-norbornyloxamide; N,N′-dimethyloxamide; N,N′-diethyloxamide; N,N′-diisopropyloxamide; N,N′-diphenyloxamide; N,N′-dibenzyloxamide; N,N′-dicyclohexyloxamide; and N,N′-dinorbornyloxamide.

O Valence Stabilizer #21: Examples of squaric acids and derivatives thereof (O—O Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: deltic acid; squaric acid; croconic acid; and rhodizonic acid.

O Valence Stabilizer #22: Examples of dicarboxylic acids, bis(dicarboxylic acids), poly(dicarboxylic acids), and derivatives thereof (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: oxalic acid; malonic acid; succinic acid; diphenyl oxalate; diphenyl malonate; and diphenyl succinate.

O Valence Stabilizer #23: Examples of carbamates, bis(carbamates), and poly(carbamates) (including N-hydroxycarbamates and N-mercaptocarbamates) (O—O Bidentates, O—O Tridentates, and O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dimethylcarbamate (dmc); di(trifluorodimethyl)carbamate; ethyl carbamate; diethylcarbamate (dec); dipropylcarbamate; diisopropylcarbamate; dibutylcarbamate; ditertbutylcarbamate; dicyanamidocarbamate; diphenylcarbainate; di(pentafluorophenyl)carbamate; dibenzylcarbamate; dinaphthylcaibamate; dicyclohexylcarbamate; dinorbornylcarbamate; diadamantylcarbamate; pyrrolidinocarbamate (pyrc); piperidinocarbamate (pipc); morpholinocarbamate (morc); thiamorpholinocarbamate; 3-pyrrolinocarbamate; pyrrolocarbamate; oxazolocarbamate; isoxazolocarbamate; thiazolocarbamate; isothiazolocarbamate; indolocarbamate; carbazolocarbamate; pyrazolinocarbamate; imidazolinocarbamate; pyrazolocarbamate; imidazolocarbamate; indazolocarbamate; and triazolocarbamate.

O Valence Stabilizer #24: Examples of carbimates, bis(carbimates), and poly(carbimates) (O—O Bidentates, O—O Tridentates, and O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methylcarbimate; trifluoromethylcarbimate; ethylcarbimate; propylcarbimate; isopropylcarbimate; butylcarbimate; tertbutylcarbimate; cyanocarbimate; cyanamidocarbimate; azidocarbimate; phenylcarbimate; pentafluorophenylcarbimate; benzylcarbimate; naphthylcarbimate; cyclohexylcarbimate; norbornylcarbimate; and adamantylcarbimate. [Note: Carbimates tend to stabilize lower oxidation states in metal ions.]

O Valence Stabilizer #25: Examples of cyanate ligands (O monodentates) that meet the 5 requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyanate (—OCN).

N—S Valence Stabilizer #1: Examples of diformamidine disulfides (thioperoxydicarbonimidic diamides), thioperoxytricarbonimidic diamides, thioperoxytetracarbonimidic diamides, bis(diformamidine disulfides), and poly(diformamidine disulfides) (N—S bidentates, N—N—S tridentates, or N—S tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diformamidine disulfide; methyldiformamidine disulfide; ethyldiformamidine disulfide; isopropyldiformamidine disulfide; butyldiformamidine disulfide; benzyldiformamidine disulfide; phenyldiformamidine disulfide; tolyldiformamidine disulfide; naphthyldiformamidine disulfide; cyclohexyldiformamidine disulfide; norbornyldiformamidine disulfide; adamantyldiformamidine disulfide; dimethyldiformamidine disulfide; diethyldiformamidine disulfide; diisopropyldiformamidine disulfide; dibutyldiformamidine disulfide; dibenzyldiformamidine disulfide; diphenyldiformamidine disulfide; ditolyldiformamidine disulfide; dinaphthyldiformamidine disulfide; dicyclohexyldiformamidine disulfide; dinorbornyldiformamidine disulfide; diadamantyldiformamidine disulfide; 2-S-amidinodisulfidothiazole; 2-S-amidinodisulfidooxazole; 2-S-amidinodisulfidoimidazole; 3-S-amidinodisulfidopyrazole; 3-S-amidinodisulfido-1,2,4-triazole; and 5-S-amidinodisulfidotetrazole.

N—S Valence Stabilizer #2: Examples of S-amidinodithiocarbamates, bis(S-amidinodithiocarbamates), and poly(S-amidinodithiocarbamates) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: S-amidinodithiocarbamate; N-methyl-S-amidinodithiocarbamate; N-ethyl-S-amidinodithiocarbamate; N-isopropyl-S-amidinodithiocarbamate; N-butyl-S-amidinodithiocarbamate; N-benzyl-S-amidinodithiocarbamate; N-phenyl-S-amidinodithiocarbamate; N-tolyl-S-amidinodithiocarbamate; N-naphthyl-S-amidinodithiocarbamate; N-cyclohexyl-S-amidinodithiocarbamate; N-norbornyl-S-amidinodithiocarbamate; N-adamantyl-S-amidinodithiocarbamate; N,N′-dimethyl-S-amidinodithiocarbamate; N,N′-diethyl-S-amidinodithiocarbamate; N,N′-diisopropyl-S-amidinodithiocarbamate; N,N′-dibutyl-S-amidinodithiocarbamate; N,N′-dibenzyl-S-amidinodithiocarbamate; N,N′-diphenyl-S-amidinodithiocarbamate; N,N′-ditolyl-S-amidinodithiocarbamate; N,N′-dinapbthyl-S-amidinodithiocarbamate; N,N′-dicyclohexyl-S-amidinodithiocarbamate; N,N′-dinorbornyl-S-amidinodithiocarbamate; N,N′-diadamantyl-S-amidinodithiocarbamate; etbylenebis(S-amidinodithiocarbamate); propylenebis(S-amidinodithiocarbamate); phenylenebis(S-amidinodithiocarbamate); piperazinebis(S-amidinodithiocarbamate); oxalylbis(S-amidinodithiocarbamate); malonylbis(S-amidinodithiocarbamate); succinylbis(S-amidinodithiocarbamate); phthalylbis(S-amidinodithiocarbamate); 2-S-dithiocarbamatothiazole; 2-S-dithiocarbamatooxazole; 2-S-dithiocarbamatoimidazole; 3-S-dithiocarbamatopyrazole; 3-S-dithiocarbamato-1,2,4-triazole; and 5-S-dithiocarbamatotetrazole.

N—S Valence Stabilizer #3: Examples of O-amidinothiocarbamates, bis(O-amidinothiocarbamates), and poly(O-amidinothiocarbamates) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: O-amidinothiocarbamate; N-methyl-O-amidinothiocarbamate; N-ethyl-O-amidinothiocarbamate; N-isopropyl-O-amidinothiocarbamate; N-butyl-O-amidinothiocarbamate; N-benzyl-O-amidinothiocarbamate; N-pbenyl-O-amidinothiocarbamate; N-tolyl-O-amidinothiocarbamate; N-naphthyl-O-amidinothiocarbamate; N-cyclohexyl-O-amidinothiocarbamate; N-norbornyl-O-amidinothiocarbamate; N-adamantyl-O-amidinothiocarbamate; N,N′-dimethyl-O-amidinothiocarbamate; N,N′-diethyl-O-amidinothiocarbamate; N,N′-diisopropyl-O-amidinothiocarbamate; N,N′-dibutyl-O-amdinothiocarbamate; N,N′-dibenzyl-O-amidinothiocarbamate; N,N′-diphenyl-O-amidinothiocarbamate; N,N′-ditolyl-O-amidinothiocarbamate; N,N′-dinaphthyl-O-amidinothiocarbamate; N,N′-di cyclohexyl-O-amidinothiocarbamate; N,N′-dinorbornyl-O-amidinothiocarbamate; N,N′-diadamantyl-O-amidinothiocarbamate; ethylenebis(O-amidinothiocarbamate); propylenebis(O-amidinothiocarbamate); phenylenebis(O-amidinothiocarbamate); piperazinebis(O-amidinothiocarbamate); oxalylbis(O-amidinothiocarbamate); malonylbis(O-amidinothiocarbamate); succinylbis(O-amidinothiocarbamate); phthalylbis(O-amidinothiocarbamate); 2-O-monothiocarbamatothiazole; 2-O-monothiocarbamatooxazole; 2-O-monothiocarbamatoimidazole; 3-O-monothiocarbamatopyrazole; 3-O-monothiocarbamato-1,2,4-triazole; and 5-O-monothiocarbamatotetrazole.

N—S Valence Stabilizer #4: Examples of S-amidinoperoxythiocarbamates, bis(S-amidinoperoxythiocarbamates), and poly(S-amidinoperoxythiocarbamates) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: S-amidinoperoxythiocarbamate; N-methyl-S-amidinoperoxythiocarbamate; N-ethyl-S-amidinoperoxythiocarbamate; N-isopropyl-S-amidinoperoxythiocarbamate; N-butyl-S-amidinoperoxythiocarbamate; N-benzyl-S-amidinoperoxythiocarbamate; N-phenyl-S-amidinoperoxythiocarbamate; N-tolyl-S-amidinoperoxythiocarbamate; N-naphthyl-S-amidinoperoxythiocarbamate; N-cyclohexyl-S-amidinoperoxythiocarbamate; N-norbornyl-S-amidinoperoxythiocarbamate; N-adamantyl-S-amidinoperoxythiocarbamate; N,N′-dimethyl-S-amidinoperoxythiocarbamate; N,N′-diethyl-S-amidinoperoxythiocarbamate; N,N′-diisopropyl-S-amidinoperoxythiocarbamate; N,N′-dibutyl-S-amidinoperoxythiocarbamate; N,N′-dibenzyl-S-amidinoperoxythiocarbamate; N,N′-diphenyl-S-amidinoperoxythiocarbamate; N,N′-ditolyl-S-amidinoperoxythiocarbamate; N,N′-dinaphthyl-S-amidinoperoxythiocarbamate; N,N′-dicyclohexyl-S-amidinoperoxythiocarbamate; N,N′-dinorbornyl-S-amidinoperoxythiocarbamate; N,N′-diadamantyl-S-amidinoperoxythiocarbamate; ethylenebis(S-amidinoperoxythiocarbamate); propylenebis(S-amidinoperoxythiocarbamate); phenylenebis(S-amidinoperoxythiocarbamate); piperazinebis(S-amidinoperoxythiocarbamate); oxalylbis(S-amidinoperoxythiocarbamate); malonylbis(S-amidinoperoxythiocarbamate); succinylbis(S-amidinoperoxythiocarbamate); and phthalylbis(S-amidinoperoxythiocarbamate).

N—S Valence Stabilizer #5: Examples of phosphorimidothioic acid; phosphorimidodithioic acid; phosphorimidotrithioic acid; bis(phosphorimidothioic acid); bis(phosphorimidodithioic acid); bis(phosphorimidotrithioic acid); poly(phosphorimidothioic acid); poly(phosphorimidodithioic acid); poly(phosphorimidotrithioic acid); and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphorimidothioic acid; phosphorimidodithioic acid; phosphorimidotritbioic acid; O-phenylphosphorimidothioic acid; O-benzylphosphorimidothioic acid; O-cyclohexylphosphorimidothioic acid; O-norbornylphosphorimidothioic acid; O,O′-diphenylphosphorimidothioic acid; O,O′-dibenzylphosphorimidothioic acid; O,O′-dicyclohexylphosphorimidothioic acid; and O,O′-dinorbornylphosphorimidothioic acid.

N—S Valence Stabilizer #6: Examples of phosphorothioic triamides, bis(phosphorothioic triamides), and poly(phosphorothioic triamides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphorothioic triamide; phosphorothioic trihydrazide; phosphoramidothioic dihydrazide; N-phenylphosphorothioic triamide; N-benzylphosphorothioic triamide; N-cyclohexylphosphorothioic triamide; N-norbornylphosphorothioic triamide; N,N′-diphenylphosphorothioic triamide; N,N′-dibenzylphosphorothioic triamide; N,N′-dicyclohexylphosphorothioic triamide; and N,N′-dinorbornylphosphorothioic triamide.

N—S Valence Stabilizer #7: Examples of phosphoramidotrithioic acid, phosphorodiamidodithioic acid, bis(phosphoramidotritbioic acid), bis(phosphorodiamidodithioic acid), poly(phosphoramidotrithioic acid), poly(phosphorodiamidodithioic acid), and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoramidotrithioic acid, phosphorodiamidodithioic acid, S-phenylphosphoramidotrithioic acid, S-benzylphosphoramidotrithioic acid, S-cyclohexylphosphoramidotrithioic acid, S-norbornylphosphoramidotrithioic acid, S,S′-diphenylphosphoramidotritbioic acid, S,S′-dibenzylphosphoramidotrithioic acid, S,S′-dicyclohexylphosphoramidotrithioic acid, and S,S′-dinorbornylphosphoramidotrithioic acid.

N—S Valence Stabilizer #8: Examples of phosphoramidothioic acid, phosphoramidodithioic acid, phosphorodiamidothioic acid, bis(phosphoramidothioic acid), bis(phosphoramidodithioic acid), bis(phosphorodiamidothioic acid), poly(phosphoramidothioic acid), poly(phosphoramidodithioic acid), and poly(phosphorodiamidothioic acid) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoramidothioic acid, phosphoramidodithioic acid, phosphorodiamidothioic acid, phosphorohydrazidothioic acid, phosphorohydrazidodithioic acid, phosphorodihydrazidothioic acid, phosphoramidohydrazidothioic acid, O-phenylphosphoramidothioic acid, O-benzylphosphoramidothioic acid, O-cyclobexylphosphoramidothioic acid, O-norbornylphosphoramidothioic acid, S-phenylphosphoramidodithioic acid, S-benzylphosphoramidodithioic acid, S-cyclohexylphosphoramidodithioic acid, and S-norbornylphosphoramidodithioic acid.

N—S Valence Stabilizer #9: Examples of N-thioacyl 7-aminobenzylidenimines (N—S Bidentates or N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-thioacetyl 7-methylaminobenzylidenimine; N-thioacetyl 7-phenylaminobenzylidenimine; N-thiobenzoyl 7-methylaminobenzylidenimine; and N-thiobenzoyl 7-phenylaminobenzylidenimine.

N—S Valence Stabilizer #10: Examples of thiohydroxamates (thiohydroxylamines), bis(thiohydroxamates), and poly(thiohydroxamates) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetothiohydroxamic acid; propianothiohydroxamic acid; butyrothiohydroxamic acid; crotonothiohydroxamic acid; sorbothiohydroxamic acid; benzothiohydroxamic acid; toluicthiohydroxamic acid; salicylthiohydroxamic acid; phenylacetothiohydroxamic acid; anthranilthiohydroxamic acid; nicotinethiohydroxamic acid; picolinethiohydroxamic acid; cyclohexanethiohydroxamic acid; quinoline 8-thiohydroxamic acid; cinnamylthiohydroxamic acid; oxaldithiohydroxamic acid; succinylbis-N-phenylthiohydroxamic acid; adipylbis-N-phenylthiohydroxamic acid; glyoxalthiohydroxamic acid; 2-thiophenethiocarbohydroxamic acid; thenoylthiohydroxamic acid; N-phenylbenzothiohydroxamic acid; N-tolylbenzothiohydroxamic acid; N-phenylacetothiohydroxamic acid; N-phenyl-2-thenoylthiohydroxamic acid; and N-tolyl-2-thenoylthiohydroxamic acid.

N—S Valence Stabilizer #11: Examples of alpha- or ortho-aminothiocarboxylic acids, and alpha- or ortho-aminothiodicarboxylic acids, and derivatives thereof (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-pyridinethiocarboxylic acid (thiopicolinic acid); 2-pyrazinethiocarboxylic acid; o-aminothiobenzoic acid; o-aminothionaphthoic acid; and 3,6-diaminothiophthalic acid.

N—S Valence Stabilizer #12: Examples of thiosemicarbazones, bis(thiosemicarbazones), and poly(thiosemicarbazones) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetaldehyde thiosemicarbazone; acetone thiosemicarbazone; pinacolone thiosemicarbazone; benzaldehyde thiosemicarbazone; naphthaldehyde thiosemicarbazone; norbornanone thiosemicarbazone; camphor thiosemicarbazone; nopinone thiosemicarbazone; 2-pyridinaldehyde thiosemicarbazone; salicylaldehyde thiosemicarbazone; quinolinaldehyde thiosemicarbazone; isatin dithiosemicarbazone; camphorquinone dithiosemicarbazone; camphorquinone dithiosemicarbazone; picolinaldehyde thiosemicarbazone; dipyridyl glyoxal dithiosemicarbazone; di-2-pyridyl ketone thiosemicarbazone; methyl-2-pyridyl ketone thiosemicarbazone; glyoxal dithiosemicarbazone; acetophenone thiosemicarbazone; biacetyl monoxime thiosemicarbazone; acetamidobenzaldehyde thiosemicarbazone; thymolaldothiosemicarbazone; thiophene-2-aldehyde thiosemicarbazone; phthalaldehyde dithiosemicarbazone; phthalimide dithiosemicarbazone; furaldehyde thiosemicarbazone; naphthoquinone thiosemicarbazone; phenanthrequinone thiosemicarbazone; cyclohexanedione dithiosemicarbazone; ionone thiosemicarbazone; bisthiosemicarbazone of diethyl-3,4-dioxadioate; pyridoxal alkylthiosemicarbazones; benzylidene phenylthiosemicarbazones; lawsone thiosemicarbazone; and 1-benzoin-4-phenylthiosemicarbazone (bps).

N—S Valence Stabilizer #13: Examples of thioacyl hydrazones, bis(thioacyl hydrazones), and poly(thioacyl hydrazones) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetaldehyde N-thioformylhydrazone; acetaldehyde N-thiobenzoylhydrazone; acetone N-thioformylhydrazone; acetone N-thiobenzoylhydrazone; pinacolone N-thioformylhydrazone; pinacolone N-thiobenzoylhydrazone; benzaldehyde N-thioformylhydrazone; benzaldehyde N-thiobenzoylhydrazone; naphthaldehyde N-thioformylhydrazone; naphthaldehyde N-thiobenzoylhydrazone; norbornanone N-thioformylhydrazone; norbornanone N-thiobenzoylhydrazone; camphor N-thioformylhydrazone; camphor N-thiobenzoylhydrazone; nopinone N-thioformylhydrazone; nopinone N-thiobenzoylhydrazone; 2-pyridinaldehyde N-thioformylhydrazone; 2-pyridinaldehyde N-thiobenzoylhydrazone; salicylaldehyde N-thioformylhydrazone; salicylaldehyde N-thiobenzoylhydrazone; quinolinaldehyde N-thioformylhydrazone; quinolinaldehyde N-thiobenzoylhydrazone; thiophene-2-aldehyde N-thioformylhydrazone; thiophene-2-aldehyde N-thiobenzoylhydrazone; naphthoqui none N-thioformylhydrazone; naphthoqui none N-thiobenzoylhydrazone; ionone N-thioformylhydrazone; ionone N-thiobenzoylhydrazone; benzaldehyde benzothiazolehydrazone; lawsone N-thioformylhydrazone; and lawsone N-thiobenzoylhydrazone.

N—S Valence Stabilizer #14: Examples of thiocarbazones (diazenecarbothioic hydrazides), bis(thiocarbazones), and poly(thiocarbazones) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphenylthiocarbazone (dithizone); 2-phenylthiocarbazone; dinaphthylthiocarbazone; 2-naphthylthiocarbazone; and ambazone.

N—S Valence Stabilizer #15: Examples of azo compounds with thiol or mercapto or thiocarbonyl substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, Bis[o-(HS—) or alpha- or beta-(HS—)azo compounds], or Poly[o-(HS—) or alpha- or beta-(HS—)azo compounds) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-thiolazobenzene [1-(phenylazo)-2-thiophenol]; 2,2′-dithioazobenzene; (2-thiophene)azobenzene; 1-(4-nitrophenylazo)-2-thionaphthol; 2-thiazolylazobenzene; and 2-benzothiazolylazobenzene.

N—S Valence Stabilizer #16: Examples of diazeneformothioamides, diazeneacetothioamides, bis(diazeneformothioamides), bis(diazeneacetothioamides), poly(diazeneformothioamides), and poly(diazeneacetothioamides) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformothioamide, diazeneacetothioamide, phenyldiazeneformothioamide, diphenyldiazeneformothioamide, phenyldiazeneacetothioamide, and diphenyldiazeneacetothioamide.

N—S Valence Stabilizer #117: Examples of diazenecarbothioic acids, diazenecarbodithioic acids, bis(diazenecarbothioic acids), bis(diazenecarbodithioic acids), poly(diazenecarbothioic acids), poly(diazenecarbodithioic acids) and derivatives thereof (N—S Bidentates, N—S Tetradentates, N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformothioic acid, diazeneacetothioic acid, phenyldiazeneformothioic acid, diphenyldiazeneformothioic acid, phenyldiazeneacetothioic acid, and diphenyldiazeneacetothioic acid.

N—S Valence Stabilizer #18: Examples of diazeneformothioaldehydes, diazeneacetothioaldehydes, bis(diazeneformothioaldehydes), bis(diazeneacetothioaldehydes), poly(diazeneformothioaldehydes), and poly(diazeneacetothioaldehydes) (N—S Bidentates, N—S Tetradentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformothioaldehyde, diazeneacetothioaldehyde, phenyldiazeneformothioaldehyde, diphenyldiazeneformothioaldehyde, phenyldiazeneacetothioaldehyde, and diphenyldiazeneacetothioaldehyde.

N—S Valence Stabilizer #19: Examples of diazenediformothioamides, diazenediacetothioamides, bis(diazenediformothioamides), bis(diazenediacetothioamides), poly(diazenediformothioamides), and poly(diazenediacetothioamides) (N—S Tridentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenediformodithioamide, diazenediacetodithioamide, diphenydiazenediformodithioamide, tetraphenyldiazenediformodithioamide, diphenyldiazenediacetodithioamide, and tetraphenyldiazenediacetodithioamide.

N—S Valence Stabilizer #20: Examples of diazenedicarbothioic acids, diazenedicarbodithioic acids, bis(diazenedicarbothioic acids), bis(diazenedicarbodithioic acids), poly(diazenedicarbothioic acids), poly(diazenedicarbodithioic acids) and derivatives thereof (N—S Tridentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenediformothioic acid, diazenediacetodithioic acid, phenyldiazenediformothioic acid, diphenyldiazenediformothioic acid, phenyldiazenediacetodithioic acid, and diphenyldiazenediacetodithioic acid.

N—S Valence Stabilizer #21: Examples of diazenediformothioaldehydes, diazenediacetothioaldehydes, bis(diazenediformothioaldehydes), bis(diazenediacetothioaldehydes), poly(diazenediformothioaldehydes), and poly(diazenediacetothioaldehydes) (N—S Tridentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenediformothioaldehyde, diazenediacetothioaldehyde, diphenyldiazenediformothioaldehyde, and diphenyldiazenediacetothioaldehyde.

N—S Valence Stabilizer #22: Examples of ortho-thio (or -mercapto) substituted formazans, bis(o-thio or -mercapto substituted formazans), and poly(o-thio or -mercapto substituted formazans) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1-(2-thiophenyl)-3,5-diphenylformazan; 1-(2-methylmercaptophenyl)-3,5-diphenylformazan; 1,5-bis(2-thiophenyl)-3-phenylformazan; and 5-bis(2-methylmercaptophenyl)-3-phenyl formazan.

N—S Valence Stabilizer #23: Examples of ortho-thio (or -mercapto) substituted azines (including ketazines), bis(o-thio or mercapto substituted azines), and poly(o-thio or mercapto substituted azines) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-mercapto-1-benzalazine; 2-mercapto-1-naphthalazine; and 2-mercapto-1-cyclohexanonazine.

N—S Valence Stabilizer #24: Examples of Schiff Bases with one Imine (C═N) Group and with ortho- or alpha- or beta-thio or mercapto or thiocarbonyl substitution (N—S Bidentates, N—S Tridentates, N—S Tetradentates, N—S Pentadentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-(Thiosalicylaldehydo)isopropylamine; N-(2-thiophenecarboxaldehydo)isopropylamine; N-(2-Acetylthiopheno)isopropylamine; N-(2-Thioacetophenono)isopropylamine; N-(Thiosalicylaldehydo)cyclohexylamine; N-(2-Thiophenecarboxaldehydo)cyclohexylamine; N-(2-Acetylthiopheno)cyclohexylamine; N-(2-Thioacetophenono)cyclohexylamine; N-(Thiosalicylaldehydo)aniline; N-(2-Thiophenecarboxaldehydo)aniline; N-(2-Acetylthiopheno)aniline; N-(2-Thioacetophenono)aniline; N-(Thiosalicylaldehydo)aminonorbornane; N-(2-Thiocarboxaldehydo)aminonorbornane; N-(2-Acetylthiopheno)aminonorbornane; N-(2-Thioacetophenono)aminonorbornane; 4-aminobenzylidene-3-propyl-5-mercapto-1,2,4-triazole; 4-aminocinnamalidene-3-propyl-5-mercapto-1,2,4-triazole (acpmt); 4-aminosalicylidene-3-propyl-5-mercapto-1,2,4-triazole (aspmt); 4-aminovanillidene-3-propyl-5-mercapto-1,2,4-triazole; 4-aminodimethylaminobenzylidene-3-propyl-5-mercapto-1,2,4-triazole (adpmt); cinnamylideneaminophenylthiazole; N-(2-mercaptophenyl)salicylidenimine; 2-thiophenecarboxaldehyde phenylhydrazone; 2-thiophenecarboxaldehyde 2-pyridyl hydrazone; 2-mercaptobenzaldehyde phenylhydrazone; and 2-mercaptobenzaldehyde 2-pyridyl hydrazone. Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution.

N—S Valence Stabilizer #25: Examples of Schiff Bases with two Imine (C═N) Groups and with ortho- or alpha- or beta-thio or mercapto or thiocarbonyl substitution (N—S Tridentates, N—S Tetradentates, N—S Pentadentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-(2,5-Thiophenedicarboxaldehydo)diisopropylamine; N,N′-(2,5-Thiophenedicarboxaldehydo)dicyclohexylamine; N,N′-(2,5-Thiophenedicarboxaldehydo)dianiline; N,N′-(2,5-Thiophenedicarboxaldehydo)di-aininonorbornane; N,N′-(o-Thiophthalicdialdehydo)diisopropylamine; N,N′-(o-Thiophthalicdialdehydo)dicyclohexylamine; N,N′-(o-Thiophthalicdialdehydo)dianiline; N,N′-(o-Thiophthalicdialdehydo)di-aminonorbornane; N,N′-(o-Thioformylcamphoro)diisopropylamine; N,N′-(o-Thioformylcamphoro)dicyclohexyl amine; N,N′-(o-Thioformylcamphoro)dianiline; N,N′-(o-Thioformylcamphoro)di-aminonorbornane; N,N′-(o-Thiodiacetylbenzeno)diisopropylamine; N,N′-(o-Thiodiacetylbenzeno)dicyclohexylamine; N,N′-(o-Thiodiacetylbenzeno)dianiline; N,N′-(o-Thiodiacetylbenzeno)di-aminonorbornane; N,N′-(3,6-Dithio-1,2-cyclohexanono)diisopropylamine; N,N′-(3,6-Dithio-1,2-cyclohexanono)dicyclohexylamine; N,N′-(3,6-Dithio-1,2-cyclohexanono)dianiline; N,N′-(3,6-Dithio-1,2-cyclohexanono)di-aminonorbornane; N,N′-(2,5-Diacetylthiopheno)diisopropylamine; N,N′-(2,5-Diacetylthiopheno)dicyclohexylamine; N,N′-(2,5-Diacetylthiopheno)dianiline; N,N′-(2,5-Diacetylthiopheno)di-aminonorbornane; N,N′-(Thiosalicylaldehydo)ethylenediamine; N,N′-(o-Thionaphthaldehydo)ethylenediamine; N,N′-(o-Thioacetophenono)ethylenediamine; N,N′-(Thiosalicylaldehydo)trimethylenediamine; N,N′-(o-Thionaphthaldehydo)trimethylenediamine; N,N′-(o-Thioacetophenono)trimethylenediamine; N,N′-(Thiosalicylaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Thionaphthaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Thioacetophenono)cyclohexane-1,2-diamine; N,N′-(Thiosalicylaldehydo 1,2-diaminobenzene; N,N′-(o-Thionaphthaldehydo)-1,2-diaminobenzene; and N,N′-(o-Thioacetophenono)-1,2-diaminobenzene. Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution.

N—S Valence Stabilizer #26: Examples of Schiff Bases with three Imine (C═N) Groups and with ortho- or alpha- or beta-thio or mercapto or thiocarbonyl substitution (N—S Tetradentates, N—S Pentadentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′,N″-(Thiosalicylaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(o-Thionaphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(o-Thioacetopbenono)tris(2-aminoethyl)amine. Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution.

N—S Valence Stabilizer #27: Examples of thioalkyl amines (aminothiols or aminodisulfides) and thioalkyl imines (iminothiols or iminodisulfides) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-mercapto-1-aminoethane; 2-methylmercapto-1-aminoethane; 3-mercapto-1-aminopropane; 1-mercapto-2-amino-2-methylpropane; 2-mercaptocyclohexylamine; 3-mercapto-2-aminonorbornane; 1,3-dimercapto-2-aminopropane; 1,5-dimercapto-3-aminopentane; 2,2′-diaminodiethyl sulfide; 3,3′-diaminodipropyl sulfide; 2,2′-diaminodicyclohexyl sulfide; 1,6-dimercapto-3,4-diaminohexane; 1,7-dimercapto-3,5-diaminoheptane; 1,6-diamino-3,4-dimercaptohexane; 1,7-diamino-3,5-dimercaptoheptane; tri(mercaptomethyl)amine; tri(2-mercaptoethyl)amine; dithiooxamide (rubeanic acid); 2,2′-diaminodiethyl disulfide; 3,3′-diaminodipropyl disulfide; 2,2′-diaminodicyclohexyl disulfide; 3-amino-1,5-pentanedithiodialdehyde; 3,4-diamino-1,6-hexanedithiodialdehyde; 3,5-diamino-1,7-heptanedithiodialdehyde; iminobisacetic acid; iminobispropionic acid; and bis(hydroxyethyl)aminoalkyl sulfide.

N—S Valence Stabilizer #28: Examples of thioaryl amines and thioaryl imines (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminothiophenol (2-aminobenzenethiol); 2-aminothiobenzoic acid (thioanthranilic acid); 2-aminothioanisole; 2-(methanamine)benzyl mercaptan [(2-aminomethyl)-alpha-toluenethiol] [(2-mercaptomethyl)-alpha-aminotoluene]; 1-amino-2-naphthalenethiol; 2-amino-1-naphthalenethiol; 2-amino-1-(methyldisulfido)benzene; 2,2′-di(aminomethyl)diphenylthioketone; di(2-amino)phenyl sulfide; di(2-amino)phenyl disulfide (di-ortho-aminophenyl disulfide (doapd)); 1,3-di(2-amino)phenyl-2-mercaptopropane; 1,3-di(3-amino)phenyl-2-mercaptopropane; 1,3-di(2-mercapto)phenyl-2-aminopropane; 1,3-di(3-mercapto)phenyl-2-aminopropane; 2,2′-dimercaptoiminodibenzyl; 2,2′-iminodibenzothioic acid; 2,2′-dimercaptoiminostilbene; and poly(o-aminothiophenol).

N—S Valence Stabilizer #29: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-mercaptopyrrole; 2-(methylthio)methylpyrrole; 2,5-(thiomethyl)pyrrole; 2,5-(methylthiomethyl)pyrrole; 2,6(methyldisulfidomethyl)pyrrole; imidazoline-2-thione (2-mercaptoimidazole); 2-mercaptothiazoline; 2-mercaptobenzimidazole; 2-mercaptobenzothiazole; 2-mercaptobenzoxazole; 2-thiohydantoin; di-2-pyridylthioglyoxal (2,2′-thiopyridil); bis((1-pyrazolyl)methane)sulfide; bis((1-pyrazolyl)methane)disulfide; bis(2-(1-pyrazolyl)ethane)sulfide; bis(2-(1-pyrazolyl)ethane)disulfide; bis(benzimidazolylmethane)sulfide; bis(benzimidazolylethane)sulfide; bis(benzimidazolylmethane)disulfide; bis(benzimidazolylethane)disulfide; tris(imidazolyl)methanethiol; tris(imidazolylmethane)methanethiol; N-thiomethyl-N,N-(benzimidazolylmetbane)amine; N-(2-thioethyl)-N,N-(benzimidazolylmethane)amine; N,N′-di(benzimidazolylmethane)-1,3-diamino-2-mercaptopropane; N,N,N′,N′-tetrakis(benzimidazolylmethane)-1,3-diamino-2-mercaptopropane; bis(N,N-((4-imidazolyl)methane)2-aminoethane)sulfide; bis(N,N-((4-imidazolyl)methane)2-aminoethane)disulfide; 2-aminobenzothiazole (abt); 2-phenylaminothiazole; thiohydantoin; thioxohydropyrazole; 2-mercaptobenzothiazole (mbt); 2-mercapto-1,3,4-thiadiazole; 2,5-dimercapto-1,3,4-thiadiazole (bismuthiol); 2,5-bis(alkylthio)-1,3,4-thiadiazole; 2-amino-5-mercapto-1,3,4-thiadiazole (amt); 5-mercaptotetrazole; 1-phenyl-5-mercaptotetrazole (pmt)(5-mptt); 5-mercaptotriazole; 3-mercaptotriazole; (2-benzothiazolyl)thioacetic acid; (2-benzothiazolyl)thiopropionic acid; (alkylthio)benzotriazoles; (arylthio)benzotriazoles; 2-mercaptopyrimidine; bis(5-mercapto-1,2,4-triazol-3-yl); bis(5-mercapto-1,2,4-triazol-3-yl)alkanes; 2-aminothiazolidine; thiazolidine-2-thione; 2-mercaptothiazolidine; 1-(2-mercaptoethyl)imidazoline; imidazolidine-2-thione; 4,5-dihydroxyimidazolidine-2-thione; 4-amino-5-mercapto-1,2,4-triazole; (2-benzimidazolylthio)carboxylic acids; (2-benzoxazolylthio)carboxylic acids; (2-benzothiazolylthio)carboxylic acids; (2-benzimidazolylthio)hydroxyalkyl(aryl)s; (2-benzoxazolylthio)hydroxyalkyl(aryl)s; (2-benzothiazolylthio) hydroxyalkyl(aryl)s; 2-(phenylmethylthio)benzothiazole; 2,5-bis(hydrocrarbyldithio 1,3,4-thiadiazoles; 2-(hydroarbyldithio)-5-mercapto-1,3,4-thiadiazoles; bis(dithiobi sthiadiazole); benzothi azolethione; 3-hydrazino-5-thio-1,2,4-triazole; imidazolidine-2,4-dithione; dimercaptobenzothi azole; 2-aminothiazole (atz); thiadiazole-2-thione; 5-mercaptothiadiazole-2-thione; 1,1-thiocarbonyldiimidazole; phosphosphonomethylenethio-1,3-benzothiazole (pmtbt); 4,5-dihydroxyimidazolidine-2-thione; imidazolidine-2-thione; 1,1′-thiocarbonyldiimidazole; 2,2′-dithiobis(benzothiazole); and 5,5′-dithiobis(tetrazole).

N—S Valence Stabilizer #30: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-aminomethyl-3-pyridinemethanethiol (including thiopyridoxamine); 2-mercaptopyridine; 2-(methylthio)methylpyridine; 2-(2-(methylthio)ethyl)pyridine; 2,6-(thiomethyl)pyridine; 2,6-(methylthiomethyl)pyridine; 2,6-(methyldisulfidomethyl)pyridine; 2-mercaptopyrimidine; 2-dithiomethylpyrimidine; 2-mercaptoquinoline; 8-mercaptoquinoline (thioxine); 8-methylthioquinoline; 2-mercaptoquinazoline; thioorotic acid (1,2,3,6-tetrahydro-2,6-dithiono-4-pyrimidinecarboxylic acid) (6-thiouracilcarboxylic acid); 1-methylpyrimidine-2-thione; 2-thiouracil; 2,4-dithiouracil; 6-mercaptopurine; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminomethane)sulfide; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminomethane)disulfide; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminoethane)sulfide; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminoethane)disulfide; 1,3,5-triazine-6-thione; 2-benzylmercapto-1,3,5-triazine; triazine dithiols [i.e. 6-(phenylamino)-1,3,5-triazine-2,4-dithiol (ptd); 6-aniline-1,3,5-triazine-2,4-dithiol (atd); and 2-(N,N-dialkylamino)-1,3,5-triazine-4,6-dithiol]; 2-thioquinazoline; 2-thioquinazolin-4-one; thiomorpholin-3-thione; [2-(aminomethyl)thio]pyridine; 6-mercaptopurine; dithiouracil; and 2,2′-dithiodipyridine (2,2′-dipyridyl disulfide).

N—S Valence Stabilizer #31: Examples of five-membered heterocyclic rings containing one or two sulfur atoms at least one additional nitrogen atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminothiophene; 2,5-diaminothiophene; 2-aminomethylthiophene; 2,5-di(aminomethyl)thiophene; 2-aminobenzothiophene; and 2-iminothiolane.

N—S Valence Stabilizer #32: Examples of six-membered heterocyclic rings containing one or two sulfur atoms at least one additional nitrogen atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminothiopyran; 2,6-diaminothiopyran; 2-aminomethylthiopyran; 2,6-di(aminomethyl)thiopyran; and 2-aminobenzothiopyran.

N—S Valence Stabilizer #33: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site in a separate ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-thiophene)pyrrole; 2,5-di(2-thiophene)pyrrole; 2-(2-thiopyran)pyrrole; 2,5-di(2-thiopyran)pyrrole; 2,5-di(2-pyrrole)thiophene; 2,6-di(2-pyrrole)thiopyran; and 3,5-bis(2-thienyl)-4-amino-1,2,4-triazole (2-tat).

N—S Valence Stabilizer #34: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site in a separate ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-thiadiazolyl)benzimidazole; 2-(2-thiophene)pyridine; 2,6-di(2-thiophene)pyridine; 2-(2-thiopyran)pyridine; 2,6di(2-thiopyran)pyridine; 2,5-di(2-pyridyl)thiophene; 2,6-di(2-pyridyl)thiopyran; and 2-(4-thiazolyl)benzimidazole.

N—S Valence Stabilizer #35: Examples of two-, three-, four-, six-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or sulfur (usually thiols, mercaptans, or thiocarbonyls) and are not contained in component heterocyclic rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azathiacyclobutane ([4]aneNS); azathiacyclopentane ([5]aneNS); azathiacyclohexane ([6]aneNS); azathiacycloheptane ([7]aneNS); azathiacyclooctane ([8]aneNS); azathiacyclobutene ([4]eneNS); azathiacyclopentene ([5]eneNS); azathiacyclohexene ([6]eneNS); azathiacycloheptene ([7]eneNS); azathiacyclooctene ([8]eneNS); azathiacyclobutadiene ([4]dieneNS); azathiacyclopentadiene ([5]dieneNS); azathiacyclohexadiene ([6]dieneNS); azathiacycloheptadiene ([7]dieneN S); azathiacyclooctadiene ([8]dieneNS); diazathiacyclohexane ([6]aneSN₂); diazathiacycloheptane ([7]aneSN₂); diazathiacyclooctane ([8]aneSN₂); diazathiacyclononane ([9]aneSN₂); diazathiacyclodecane ([10]aneSN₂); diazathiacycloundecane ([11]aneSN₂); diazathiacyclododecane ([12]aneSN₂); diazathiacyclohexene ([6]eneSN₂); diazathiacycloheptene ([7]eneSN₂); diazathiacyclooctene ([8]eneSN₂); diazathiacyclononene ([9]eneSN₂); diazathiacyclodecene ([10]eneSN₂); diazathiacycloundecene ([11]eneSN₂); diazathiacyclododecene ([12]eneSN₂); diazadithiacyclooctane ([8]aneS₂N₂); diazadithiacyclononane ([9]aneS₂N₂); diazadithiacyclodecane ([10]aneS₂N₂); diazadithiacycloundecane ([11]aneS₂N₂); diazadithiacyclododecane ([12]aneS₂N₂); diazadithiacyclotridecane ([13]aneS₂N₂); diazadithiacyclotetradecane ([14]aneS₂N₂); diazadithiacyclopentadecane ([15]aneS₂N₂); diazadithiacyclohexadecane ([16]aneS₂N₂); diazadithiacycloheptadecane ([17]aneS₂N₂); diazadithiacyclooctadecane ([18]aneS₂N₂); diazadithiacyclononadecane ([19]aneS₂N₂); diazadithiacycloeicosane ([20]aneS₂N₂); diazadithiacyclooctadiene ([8]dieneS₂N₂); diazadithiacyclononadiene ([9]dieneS₂N₂); diazadithiacyclodecadiene ([10]dieneS₂N₂); diazadithiacycloundecadiene ([11]dieneS₂N₂); diazadithiacyclododecadiene ([12]dieneS₂N₂); diazadithiacyclotridecadiene ([13]dieneS₂N₂); diazadithiacyclotetradecadiene ([14]dieneS₂N₂); diazadithiacyclopentadecadiene ([15]dieneS₂N₂); diazadithiacyclohexadecadiene ([16]dieneS₂N₂); diazadithiacycloheptadecadiene ([17]dieneS₂N₂); diazadithiacyclooctadecadiene ([18]dieneS₂N₂); diazadithiacyclononadecadiene ([19]dieneS₂N₂); diazadithiacycloeicosadiene ([20]dieneS₂N₂); and tetramethyldithiahexaazacyclobidecanehexaene (mtab).

N—S Valence Stabilizer #36: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in component heterocyclic rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiopyrandipyridines; dithiophenedipyrroles; trithiopyrantripyridines; trithiophenetripyrroles; tetrathiopyrantetrapyridines; and tetrathiophenetetrapyrroles.

N—S Valence Stabilizer #37: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in a combination of heterocyclic rings and amine, imine, thiol, mercapto, or thiocarbonyl groups (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azathiatetraphyrins; diazadithiatetraphyrins; azathiahexaphyrins; diazadithiahexaphyrins; and triazatrithiahexaphyrins.

N—O Valence Stabilizer #1: Examples of N-hydroxy (or N,N′-dihydroxy)amidines and N-hydroxy (or N,N′-dihydroxy)diamidines (N—O bidentates, N—O tridentates, or N—O tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-hydroxy-N,N′-dimethylfonmamidine; N-hydroxy-N,N′-diethylformamidine; N-hydroxy-N,N′-diisopropylformamidine; N-hydroxy-N,N′-dibutylfonmamidine; N-hydroxy-N,N′-diphenylformamidine; N-hydroxy-N,N′-dibenzylformamidine; N-hydroxy-N,N′-dinaphthylformamidine; N-hydroxy-N,N′-dicyclohexylformamidine; N-hydroxy-N,N′-dinorbornylformamidine; N-hydroxy-N,N′-diadamantylformamidine; N-hydroxy-N,N′-dianthraquinonylformamidine; N-hydroxy-N,N′-dimethylacetamidine; N-hydroxy-N,N′-diethylacetamidine; N-hydroxy-N,N′-diisopropylacetamidine; N-hydroxy-N,N′-dibutylacetamidine; N-hydroxy-N,N′-diphenylacetamidine; N-hydroxy-N,N′-dibenzylacetamidine; N-hydroxy-N,N′-dinaphthylacetamidine; N-hydroxy-N,N′-dicyclohexylacetamidine; N-hydroxy-N,N′-dinorbornylacetamidine; N-hydroxy-N,N′-diadamantylacetamidine; N-hydroxy-N,N′-dimethylbenzamidine; N-hydroxy-N,N′-diethylbenzamidine; N-hydroxy-N,N′-diisopropylbenzamidine; N-hydroxy-N,N′-dibutylbenzamidine; N-hydroxy-N,N′-diphenylbenzamidine; N-hydroxy-N,N′-dibenzylbenzamidine; N-hydroxy-N,N′-dinaphthylbenzamidine; N-hydroxy-N,N′-dicyclohexylbenzamidine; N-hydroxy-N,N′-dinorbornylbenzamidine; N-hydroxy-N,N′-diadamantylbenzamidine; N-hydroxy-N,N′-dimethyltoluamidine; N-hydroxy-N,N′-diethyltoluamidine; N-hydroxy-N,N′-diisopropyltoluamidine; N-hydroxy-N,N′-dibutyltoluamidine; N-hydroxy-N,N′-diphenyltoluamidine; N-hydroxy-N,N′-dibenzyltoluamidine; N-hydroxy-N,N′-dinaphthyltoluamidine; N-hydroxy-N,N′-dicyclohexyltoluamidine; N-hydroxy-N,N′-dinorbornyltoluamidine; N-hydroxy-N,N′-diadamantyltoluamidine; N,N-dihydroxyoxalic diamidine; N,N′-dihydroxymalonic diamidine; N,N′-dihydroxysuccinic diamidine; N,N′-dihydroxyglutaric diamidine; N,N′-dihydroxyadipic diamidine; N,N′-dihydroxypimelic diamidine; N,N′-dihydroxysuberic diamidine; N,N′-dihydroxyphthalic diamidine; N,N′-dihydroxyterephthalic diamidine; N,N′-dihydroxyisophthalic diamidine; N,N′-dihydroxypiperazine diamidine.

N—O Valence Stabilizer #2: Examples of guanylureas, guanidinoureas, bis(guanylureas), bis(guanidinoureas) poly(guanylureas), and poly(guanidinoureas) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: guanylurea (amidinourea)(dicyandiamidine); guanidinourea; methylguanylurea; ethylguanylurea; isopropylguanylurea; butylguanylurea; benzylguanylurea; phenylguanylurea; tolylguanybrea; naphthylguanylurea; cyclohexylguanylurea; norbornylguanylurea; adamantylguanylurea; dimethylguanylurea; diethylguanylurea; diisopropylguanylurea; dibutylguanylurea; dibenzylguanylurea; diphenylguanylurea; ditolylguanylurea; dinaphthylguanylurea; dicyclohexylguanylurea; dinorbornylguanylurea; diadamantylguanylurea; ethylenebis(guanylurea); propylenebis(guanylurea); phenylenebis(guanylurea); piperazinebis(guanylurea); oxalylbis(guanylurea); malonylbis(guanylurea); succinylbis(guanylurea); phthalylbis(guanylurea); 2-ureidothiazole; 2-ureidooxazole; 2-ureidoimidazole; 3-ureidopyrazole; 3-ureido-1,2,4-triazole; and 5-ureidotetrazole.

N—O Valence Stabilizer #3: Examples of amidinoamides, guanidinoamides, bis(amidinoamides), bis(guanidinoamides), poly(amidinoamides), and poly(guanidinoamides) (including both N-amidinoamides and 2-amidinoacetamides) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: amidinoacetamide (1-acetylguanidine); guanidinoacetamide; amidinopropanamide; amidinobutanamide; amidinobenzamide; amidinotoluamide; amidinocyclohexamide; N-methylamidinoacetamide; N-ethylamidinopropanamide; N-propylamidinobutanamide; N-phenylamidinobenzamide; N-tolylamidinotoluamide; N-cyclohexylamidinocyclohexamide; bis(amidinooxamide); bis(amidinomalonamide); bis(amidinosuccinamide); bis(amidinophthalamide); 2-amidinoacetamide (malonamamidine); N-methyl-2-amidinoacetamide; N-ethyl-2-amidinoacetamide; N-phenyl-2-amidinoacetamide; N-benzyl-2-amidinoacetamide; N-cyclohexyl-2-amidinoacetamide; N,N′-dimethyl-2-amidinoacetamide; N,N′-diethyl-2-amidinoacetamide; N,N′-diphenyl-2-amidinoacetamide; N,N′-dibenzyl-2-amidinoacetamide; N,N′-dicyclohexyl-2-amidinoacetamide; 2-N-acylaminothiazole; 2-N-acylaminooxazole; 2-N-acylaminoimidazole; 3-N-acylaminopyrazole; 3-N-acylamino-1,2,4-triazole; and 5-N-acyl aminotetrazole.

N—O Valence Stabilizer #4: Examples of imidoylamides, bis(imidoylamides), and poly(imidoylamides) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetimidoylacetamide; acetimidoylpropanamide; acetimidoylbutanamide; acetimidoylbenzamide; acetimidolytoluamide; acetimidoylcyclohexamide; propimidoylpropanamide; butimidoylbutanamide; benzimidoylbenzamide; ethylenebis(acetimidoylacetamide); propylenebis(acetimidoylacetamide); and phenylenebis(acetimidoylacetamide).

N—O Valence Stabilizer #5: Examples of O-amidinocarbamates, bis(O-amidinocarbamates), and poly(O-amidinocarbamates) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: O-amidinocarbamate; N-methyl-O-amidinocarbamate; N-ethyl-O-amidinocarbamate; N-isopropyl-O-amidinocarbamate; N-butyl-O-amidinocarbamate; N-benzyl-O-amidinocarbamate; N-phenyl-O-amidinocarbamate; N-tolyl-O-amidinocarbamate; N-naphthyl-O-amidinocarbamate; N-cyclohexyl-O-amidinocarbamate; N-norbornyl-O-amidinocarbamate; N-adamantyl-O-amidinocarbamate; N,N′-dimethyl-O-amidinocarbamate; N,N′-diethyl-O-amidinocarbamate; N,N′-diisopropyl-O-amidinocarbamate; N,N′-dibutyl-O-amidinocarbamate; N,N′-dibenzyl-O-amidinocarbamate; N,N′-diphenyl-O-amidinocarbamate; N,N′-ditolyl-O-amidinocarbamate; N,N′-dinaphthyl-O-amidinocarbamate; N,N′-dicyclohexyl-O-amidinocarbamate; N,N′-dinorbornyl-O-amidinocarbamate; N,N′-diadamantyl-O-amidinocarbamate; ethylenebis(O-amidinocarbamate); propylenebis(O-amidinocarbamate); phenylenebis(O-amidinocarbamate); piperazinebis(O-amidinocarbamate); oxalylbis(O-amidinocarbamate); malonylbis(O-amidinocarbamate); succinylbis(O-amidinocarbamate); phthalylbis(O-amidinocarbamate); 2-O-carbamatothiazole; 2-O-carbamatooxazole; 2-O-carbamatoimidazole; 3-O-carbamatopyrazole; 3-O-carbamato-1,2,4-triazole; and 5-carbamatotetrazole.

N—O Valence Stabilizer #6; Examples of S-amidinothiocarbamates, bis(S-amidinothiocarbamates), and poly(S-amidinothiocarbamates) (N-O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: S-amidinothiocarbamate; N-methyl-S-amidinothiocarbamate; N-ethyl-S-amidinothiocarbamate; N-isopropyl-S-amidinothiocarbamate; N-butyl-S-amidinothiocarbamate; N-benzyl-S-amidinothiocarbamate; N-phenyl-S-amidinothiocarbamate; N-tolyl-S-amidinothiocarbamate; N-naphthyl-S-amidinothiocarbamate; N-cyclohexyl-S-amidinothiocarbamate; N-norbornyl-S-amidinothiocarbamate; N-adamantyl-S-amidinothiocarbamate; N,N′-dimethyl-S-amidinothiocarbamate; N,N′-diethyl-S-amidinothiocarbamate; N,N′-diisopropyl-S-amidinothiocarbamate; N,N′-dibutyl-S-amidinothiocarbamate; N,N′-dibenzyl-S-amidinothiocarbamate; N,N′-diphenyl-S-amidinothiocarbamate; N,N′-ditolyl-S-amidinothiocarbamate; N,N′-dinaphthyl-S-amidinothiocarbamate; N,N′-dicyclohexyl-S-amidinothiocarbamate; N,N′-dinorbornyl-S-amidinothiocarbamate; N,N′-diadamantyl-S-amidinothiocarbamate; ethylenebis(S-amidinothiocarbamate); propylenebis(S-amidinothiocarbamate); phenylenebis(S-amidinothiocarbamate); piperazinebis(S-amidinothiocarbamate); oxalylbis(S-amidinothiocarbamate); malonylbis(S-amidinothiocarbamate); succinylbis(S-amidinothiocarbamate); phthalylbis(S-amidinothiocarbamate); 2-O-monothiocarbamatothiazole; 2-O-monothiocarbamatooxazole; 2-O-monothiocarbamatoimidazole; 3-O-monothiocarbamatopyrazole; 3-O-monothiocarbamato-1,2,4-triazole; and 5-O-monothiocarbamatotetrazole.

N—O Valence Stabilizer #7: Examples of diimidosulfuric acid, bis(diimidosulfuric acid), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diimidosulfuric acid; O-phenyldiimidosulfuric acid; O-benzyldiimidosulfuric acid, O-cyclohexyldiimidosulfuric acid, O-norbornyldiimidosulfuric acid, O,O′-diphenyldiimidosulfuric acid; O,O′-dibenzyldiimidosulfuric acid, O,O′-dicyclohexyldiimidosulfuric acid, and O,O′-dinorbornyldiimidosulfuric acid.

N—O Valence Stabilizer #8: Examples of phosphorimidic acid, bis(phosphorimidic acid); and poly(phosphorimidic acid), and derivatives thereof (N—O Bidentates, N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphorimidic acid; O-phenylphosphorimidic acid; O-benzylphosphorimidic acid; O-cyclohexylphosphorimidic acid; O-norbornylphosphorimidic acid; O,O′-diphenylphosphorimidic acid; O,O′-dibenzylphosphorimidic acid; O,O′-dicyclohexylphosphorimidic acid; and O,O′-dinorbornylphosphorimidic acid.

N—O Valence Stabilizer #9: Examples of phosphoric triamides, bis(phosphoric triamides), and poly(phosphoric triamides) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoric triamide; phosphoramidic dihydrazide; N-phenylphosphoric triamide, N-benzylphosphoric triamide; N-cyclohexylphosphoric triamide; N-norbornylphosphoric triamide; N,N′-diphenylphosphoric triamide, N,N′-dibenzylphosphoric triamide; N,N′-dicyclohexylphosphoric triamide; and N,N′-dinorbornylphosphoric triamide.

N—O Valence Stabilizer #10: Examples of phosphoramidic acid, phosphorodiamidic acid, bis(phosphoramidic acid), bis(phosphorodiamidic acid), poly(phosphoramidic acid), poly(phosphorodiamidic acid), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoramidic acid, phosphorodiamidic acid, phosphoramidohydrazidic acid; phosphorohydrazidic acid; phosphorodihydrazidic acid; O-phenylphosphoramidic acid; O-benzylphosphoramidic acid; O-cyclohexylphosphoramidic acid; O-norbornylphosphoramidic acid; O,O′-diphenylphosphoramidic acid; O,O′-dibenzylphosphoramidic acid; O,O′-dicyclohexylphosphoramidic acid; and O,O′-dinorbornylphosphoramidic acid.

N—O Valence Stabilizer #11: Examples of N-acyl 7-aminobenzylidenimines (N—O Bidentates or N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-acetyl 7-methylaminobenzylidenimine; N-acetyl 7-phenylaminobenzylidenimine; N-benzoyl 7-methylaminobenzylidenimine; and N-benzoyl 7-phenylaminobenzylidenimine.

N—O Valence Stabilizer #12: Examples of oximes, dioximes, and poly(oximes) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetaldoxime (Hado); acetoxime (acetone oxime)(Hato); butanone oxime; pentanone oxime; hexanone oxime; pinacolone oxime; heptanone oxime; octanone oxime; cyclopentanone oxime; cyclohexanone oxime; cycloheptanone oxime; cyclooctanone oxime; cyclopentanedione dioxime; cyclohexanedione dioxime; cycloheptanedione dioxime; cyclooctanedione dioxime; isatin dioxime; benzaldehyde oxime; naphthaldehyde oxime; norbornanone oxime; camphor oxime; dimethylglyoxime (H₂DMG); diethylglyoxime; diisopropylglyoxime; ditertbutylglyoxime; dicyanoglyoxime; dicyanamidoglyoxime; diphenylglyoxime (Hdfg); dibenzylglyoxime; dicyclohexylglyoxime; dinorbornylglyoxime; camphorquinone dioxime (Hcqd); nopinoquinone dioxime (Hnqd); butyraldoxime; propionaldoxime; furildioxime; and thienyldioxime.

N—O Valence Stabilizer #13: Examples of carbonyl oximes, bis(carbonyl oximes), and poly(carbonyl oximes) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diacetyl monoxime (2,3-butanedione monoxime); benzil monoxime (1,2-diphenylethanedione monoxime); 1,2-dicyclohexylethanedione monoxime; 1,2-(trifluoromethyl)ethanedione monoxime; 1,2-dinorbornylethanedione monoxime; cyclopentanedione monoxime; cyclohexanedione monoxime; cycloheptanedione monoxime; cyclooctanedione monoxime; camphorquinone oxime; 3-hydroxyiminopentane-2,4-dione; and 4-isonitrosopyralozone.

N—O Valence Stabilizer #14: Examples of imine oximes, bis(imine oximes), and poly(imine oximes) (including 2-nitrogen heterocyclic oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-(methylimino)butan-2-one oxime; 4-(methylimino)hexan-3-one oxime; 1,2-dipbenyl-2-(methylimino)ethan-1-one oxime; 1,2-diphenyl-2-(phenylimino)ethan-1-one oxime; 1,2-dicyclohexyl-2-(methylimino)ethan-1-one oxime; 1,2-dicyclohexyl-2-(cyclohexylimino)ethan-1-one oxime; 1,2-dinorbornyl-2-(methylimino)ethan-1-one oxime; N,N′-methylenebis-(3-iminobutan-2-one oxime); N,N′-methylenebis-(4-iminohexan-3-one oxime); N,N′-methylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime); N,N′-methylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime); N,N′-methylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime); N,N′-ethylenebis-(3-iminobutan-2-one oxime); N,N′-ethylenebis-(4-iminohexan-3-one oxime); N,N′-ethylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime); N,N′-ethylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime); N,N′-ethylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime); N,N′-propylenebis-(3-iminobutan-2-one oxime); N,N′-propylenebis-(4-iminohexan-3-one oxime); N,N′-propylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime); N,N′-propylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime); N,N′-propylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime); diacetylazine oxime (Hazio); 2-pyridinaldoxime (Hpao); methyl 2-pyridyl ketone oxime; ethyl 2-pyridyl ketoxime; phenyl 2-pyridyl ketone oxime (Hppk); benzyl 2-pyridyl ketoxime; di(2-pyridyl) ketone oxime; methyl 2-pyrrolyl ketone oxime; ethyl 2-pyrrolyl ketone oxime; phenyl 2-pyrrolyl ketone oxime; di(2-pyrrolyl) ketone oxime; and tris(2-aldoximo-6-pyridyl)phosphine.

N—O Valence Stabilizer #15: Examples of hydroxy oximes, bis(hydroxy oximes), and poly(hydroxy oximes) (including 2-oxygen heterocyclic oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-hydroxybutan-2-one oxime; 4-hydroxyhexan-3-one oxime; benzoin oxime (bo)(1,2-diphenyl-2-hydroxyethanone oxime); 1,2-di(trifluoromethyl)-2-hydroxyethanone oxime; 1,2-dicyclohexyl-2-hydroxyethanone oxime; 1,2-dinorbornyl-2-hydroxyethanone oxime; salicylaldoxime (so)(saldox); 2-hydroxy-1-naphthaldehyde oxime; 2-furanaldoxime; furildioxime; methyl 2-furanyl ketone oxime; ethyl 2-furanyl ketoxime; phenyl 2-furanyl ketone oxime; benzyl 2-furanyl ketoxime; di(2-furanyl) ketone oxime; and 2,5-(oximinomethyl)phenol.

N—O Valence Stabilizer #16: Examples of amino oximes, bis(amino oximes), and poly(amino oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-(methylamino)butan-2-one oxime (HMeabo); 4-(methylamino)hexan-3-one oxime (HEtabo); 1,2-diphenyl-2-(methylamino)ethanone oxime (HPhabo); 1,2-diphenyl-2-(phenylamino)ethanone oxime; 1,2-dicyclohexyl-2-(methylamino)ethanone oxime (HcyHxabo); 1,2-dicyclohexyl-2-(cyclohexylamino)ethanone oxime; 1,2-di(trifluoromethyl)-2-(methylamino)ethanone oxime; 1,2-dinorbornyl-2-(methylamino)ethanone oxime (HNorbabo); N,N′-ethylenebis-(3-aminobutan-2-one oxime)(Haboen); N,N′-ethylenebis-(4-aminohexan-3-one oxime); N,N′-ethylenebis-(1,2-diphenyl-2-aminoethanone oxime); N,N′-ethylenebis-(1,2-dicyclohexyl-2-aminoethanone oxime); N,N′-ethylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime); N,N′-ethylenebis-(1,2-dinorbornyl-2-aminoethanone oxime); N,N′-propylenebis-(3-aminobutan-2-one oxime)(Habopn); N,N′-propylenebis-(4-aminohexan-3-one oxime); N,N′-propylenebis-(1,2-diphenyl-2-aminoethanone oxime); N,N′-propylenebis-(1,2-dicyclohexyl-2-aminoethanone oxime); N,N′-propylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime); N,N′-propylenebis-(1,2-dinorbornyl-2-aminoethanone oxime); 2,2′-iminobis(acetamidoxime); 1-diethylamino-3-butanoxime; and di-2-pyridyl ketone oxime.

N—O Valence Stabilizer #17: Examples of amido oximes, bis(amido oximes), and poly(amido oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: formamide oxime; acetamide oxime; propanamide oxime; butanamide oxime; benzamide oxime (Hbamox); naphthamide oxime; diformamide dioxime; salicylamide oxime; and 4-imidazolamide oxime.

N—O Valence Stabilizer #18: Examples of azo oximes, bis(azo oximes), and poly(azo oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetaldehyde phenylhydrazone oxime; propionaldehyde phenylhydrazone oxime; and benzaldehyde phenylhydrazone oxime. Also includes hydrazone oximes.

N—O Valence Stabilizer #19: Examples of 2-nitrosophenols (o-quinone monoximes) (N—O Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-nitrosophenol; 1-nitroso-2-naphthol (Honn); 2-nitroso-1-naphthol (Htnn); 3-nitrosopyrocatechol; 3,6-dinitrosopyrocatechol; 2-nitrosoresorcinol; 2,4-dinitrosoresorcinol; 2,4,6-trinitrosoresorcinol; 2-nitrosohydroquinone; 2,6-dinitrosohydroquinone; 2,3,5,6-tetranitrosohydroquinone; 4-nitrosopyrogallol; 4,6-dinitrosopyrogallol; 2-nitrosophloroglucinol; 2,4,6-trinitrosophloroglucinol; 7-nitroso-6-hydroxyindazole; Pigment Green 12 (C.I. 10020); Naphthol Green; and nitroso-R-salt.

N—O Valence Stabilizer #20: Examples of 2-nitrophenols (N—O Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-nitrophenol; 2,3-dinitrophenol; 2,4-dinitrophenol; 2,5-dinitrophenol; 2,6-dinitrophenol; 2,4,6-trinitrophenol (picric acid); 2-amino-4,6-dinitrophenol (picramic acid); 1-nitro-2-naphthol; 2-nitro-1-naphthol; 3-nitropyrocatechol; 3,6-dinitropyrocatechol; 2-nitroresorcinol; 2,4-dinitroresorcinol; 2,4,6-trinitroresorcinol (styphnic acid); 2-nitrohydroquinone; 2,6-dinitrohydroquinone; 2,3,5,6-tetranitrohydroquinone; 4-nitropyrogallol; 4,6-dinitropyrogallol; 2-nitrophloroglucinol; 2,4,6-trinitrophloroglucinol; dinitrocresol; 7-nitro-6-hydroxyindazole; Dinoseb; Eosin; Naphthol Yellow; and Martius Yellow.

N—O Valence Stabilizer #21: Examples of hydroxamates (hydroxylamines), bis(hydroxamates), and poly(hydroxamates) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetohydroxamic acid; propianohydroxamic acid; butyrohydroxamic acid; crotonohydroxamic acid; sorbohydroxamic acid; benzohydroxamic acid (BH₂); toluichydroxamic acid; salicylhydroxamic acid (SH₂); phenylacetohydroxamic acid (PhH₂); anthranilhydroxamic acid (AnH₂); nicotinehydroxamic acid (NiCH₂); picolinehydroxamic acid; cyclohexanehydroxamic acid (CH₂); quinoline 8-hydroxamic acid (QH₂); cinnamylhydroxamic acid (CnH₂); oxaldihydroxamic acid (OxalH₂); succinylbis-N-phenylhydroxamic acid (SuH₂); adipylbis-N-phenylhydroxamic acid (AdH₂); glyoxalhydroxamic acid (GH₂); 2-tbiophenecarbohydroxamic acid; thenoylhydroxamic acid; N-phenylbenzohydroxamic acid; N-tolylbenzohydroxamic acid; N-phenylacetohydroxamic acid; N-phenyl-2-thenoylhydroxamic acid; N-tolyl-2-thenoylhydroxamic acid; and polyhydroxamic acids.

N—O Valence Stabilizer #22: Examples of N-nitrosohydroxylamines, bis(N-nitrosohydroxylamines), and poly(N-nitrosohydroxylamines) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-nitrosophenylhydroxylamine (cupferron); N-nitrosonaphthylhydroxylamine (neocupferron); N-nitrosoanthracylhydroxylamine; N-nitroso(2-pyridyl)hydroxylamine; and N-nitroso(2-thiophenyl)hydroxylamine.

N—O Valence Stabilizer #23: Examples of amino acids, ortho-aminocarboxylic acids, peptides, polypeptides, and proteins [N—O Bidentates, N—O Tridentates, and N—O Tetradentates; possibly S—O dentates for sulfur-contg. examples such as penicillamine and cystine] that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: alanine (Ala); arginine (Arg); asparagine (Asn); aspartic acid (Asp); cysteine (Cys); cystine (Cys or Cys.Cys); dihydroxyphenylalanine (Dopa); glutamic acid (Glu); glutamine (Gin); glycine (Gly); histidine (His); isoleucine (Ile); leucine (Leu); lysine (Lys); methionine (Met); penicillamine (Pen); phenylalanine (Phe); tolylalanine (tala); proline (Pro); sarcosine; serine (Ser); threonine (Thr); tryptophan (Trp); tyrosine (Tyr); and valine (Val) as amino acid examples; 2-pyridinecarboxylic acid (picolinic acid), 2-pyrazinecarboxylic acid, 2,3-dicarboxypyrazine, and anthranilic acid as ortho-aminocarboxylic acid examples; Gly-GluO; Hgly-Gly; Gly-MetO; Met-GlyO; Gly-TyrO; Ala-H is O; Gly-His-GlyO; Gly-Gly-His; Gly-Leu-TyrO; penta-GlyO; His-His; triaminoisobutyrate; tetra-GlyO; Pro-Gly; and Gly-Met as peptide examples; and azurin, carbonic anhydrase C; carboxypeptidase; concanavalin A; cytochrome b; cytochrome c; erythrocruorin; ferredoxin; haemerythrin; haemoglobin; myoglobin; parvalbumin; albumin; plastocyanin; rubredoxin; superoxide dismutase; thermolysin; and trysin as protein examples; N-acylamino acids; aminocaproic acid; and 3,5-diiodotyrosine.

N—O Valence Stabilizer #24: Examples of amides, bis(amides), and poly(amides), including lactams (N—O bidentates, N—O tridentates, and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetamide; propionamide; butanamide; benzamide (benzoylamide)(1-phenylformamide); 1-naphthylformamide; toluamide; 1-cyclohexylformamide); 1-norbornylformamide; 1-adamantylform amide; N,N-dimethylformamide (DMF)(DMFA); N,N-dimethylacetamide (DMAC); N,N-dimethylbenzamide; N,N-diethylformamide; N,N-diethylacetamide; decanamide; dodecanamide; tetradecanamide; hexadecanamide; octadecanamide; lactobionic acid amide; (hydroxyalkylthio)succinamides; (mercaptoalkoxy)succinamides; polycaproamides; glycinamide; aminoalkylanilides; amidopolyamines (apa); bis(1-phenylethylamide); oxalic semiamide; malonic semiamide; succinic semiamide; bis(1,1′-benzotriazolyl)dicarboxamide; nicotinamide; acetanilide (N-phenylacetamide); formanilide (N-phenylformamide); benzanilide (N-phenylbenzamide); N-methylformanilide; acetanilide; nicotinanilide; 4′-hydroxyacetanilide (acetaminophen); 2-pyrrolidone; methyl-2-pyrrolidone (NMP); 2-piperidone (valerolactam); caprolactam; polymethylenepolyamine dipropionamide; polyacrylamides; polypyrrolidones [including polyvinylpyrrolidone (povidone)(PVP)]; pyrazolidinones; pyrazolones; diazepinones; N-alkylazaalkene lactams; and N-(2-hydroxyalkyl)azaalkene lactams.

N—O Valence Stabilizer #25: Examples of semicarbazones, bis(semicarbazones), and poly(semicarbazones) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetaldehyde semicarbazone; acetone semicarbazone; pinacolone semicarbazone; benzaldehyde semicarbazone; naphthaldehyde semicarbazone; norbornanone semicarbazone; camphor semicarbazone; nopinone semicarbazone; 2-pyridinaldehyde semicarbazone; salicylaldehyde semicarbazone; quinolinaldehyde semicarbazone; isatin disemicarbazone; camphorquinone disemicarbazone; camphorquinone disemicarbazone; picolinaldehyde semicarbazone; dipyridyl glyoxal disemicarbazone; di-2-pyridyl ketone semicarbazone; methyl-2-pyridyl ketone semicarbazone; glyoxal disemicarbazone; acetophenone semicarbazone; biacetyl monoxime semicarbazone; acetamidobenzaldehyde semicarbazone; thymolaldosemicarbazone; thiophene-2-aldehyde semicarbazone; phthalaldehyde disemicarbazone; phthalimide disemicarbazone; furaldehyde semicarbazone; naphthoquinone semicarbazone; phenanthrequinone semicarbazone; cyclohexanedione disemicarbazone; ionone semicarbazone; bissemicarbazone of diethyl-3,4-dioxadioate; and lawsone semicarbazone.

N—O Valence Stabilizer #26: Examples of acyl hydrazones, bis(acyl hydrazones), and poly(acyl hydrazones) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetaldehyde N-formylhydrazone; acetaldehyde N-benzoylhydrazone; acetone N-formylhydrazone; acetone N-benzoylhydrazone; pinacolone N-formylhydrazone; pinacolone N-benzoylhydrazone; benzaldehyde N-formylhydrazone; benzaldehyde N-benzoylhydrazone; naphthaldehyde N-formylhydrazone; naphthaldehyde N-benzoylhydrazone; norbornanone N-formylhydrazone; norbornanone N-benzoylhydrazone; camphor N-formylhydrazone; camphor N-benzoylhydrazone; nopinone N-formylhydrazone; nopinone N-benzoylhydrazone; 2-pyridinaldehyde N-formylhydrazone; 2-pyridinalde hyde N-benzoylhydrazone; salicylaldehyde N-formylhydrazone; salicylaldehyde N-benzoylhydrazone; quinolinaldehyde N-formylhydrazone; quinolinaldehyde N-benzoylhydrazone; furan-2-aldehyde N-formylhydrazone; furan-2-aldehyde N-benzoylhydrazone; naphthoquinone N-formylhydrazone; naphthoquinone N-benzoylhydrazone; ionone N-formylhydrazone; ionone N-benzoylhydrazone; lawsone N-formylhydrazone; and lawsone N-benzoylhydrazone.

N—O Valence Stabilizer #27: Examples of carbazones (diazenecarboxylic hydrazides), bis(carbazones), and poly(carbazones) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphenylcarbazone; 2-phenylcarbazone; dinaphthylcarbazone; and 2-naphthylcarbazone.

N—O Valence Stabilizer #28: Examples of azo compounds with hydroxyl or carboxy or carbonyl substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, Bis[o-(HO—) or alpha- or beta-(HO—)azo compounds], or Poly[o-(HO—) or alpha- or beta-(HO—)azo compounds) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-hydroxyazobenzene [1-(phenylazo)-2-phenol]; 2,2′-dihydroxyazobenzene (o,o′-dihydroxyazobenzene); (2-furan)azobenzene; Direct Blue 2B; 1-(4-nitrophenylazo)-2-naphthol; 1-(2-hydroxyphenylazo)-2-naphthol; 1-(2-methoxyphenyl azo)-2-naphthol; pyridineazo-2-naphthol (PAN); pyridineazoresorcinol (PAR); 1-phenyl-4-(2-hydroxyphenylazo)-5-pyrazolone; 1-phenyl-4-(2-methoxyphenylazo)-5-pyrazolone; o-hydroxy-o′-(beta-aminoethylamino)azobenzene; 2-hydroxy-2′-methoxymethyleneoxyazobenzene; methyl red; turquoise blue (reactive blue); sunset yellow; amaranth; tartrazine; Eriochrome Black T; tropeolins; Allura Red; amaranth; Acid Alizarin Violet N; Acid Blue 29; Acid Orange 8, 63, and 74; Acid Red 1, 4, 8, 37, 88, 97, 114, 151, and 183; Acid Violet 7; Acid Yellow 25, 29, 34, 42, 76, and 99; Brilliant Black BN; Brilliant Crocein; Bordeaux R; Calcion; Chicago Sky Blue; Chromotrope; Cibacron Brilliant Red; Cibacron Brilliant Yellow; Crocein Orange; Crystal Scarlet; Calmagite; Direct Blue 71; Direct Red 23, 80, and 81; Direct Violet 51; Direct Yellow 8 and 27; Fast Black; Flavazin; Mordant Blue 9; Mordant Brown 1 and 33; Napthol Blue Black; New Coccine; Nitrazine Yellow; Nitrosulfonazo III; Orange II; Orange G, OT, and B; Ponceau 3R and SX; Polar Yellow; 2-oxazolylazobenzene; and 2-benzoxazolylazobenzene.

N—O Valence Stabilizer #29: Examples of diazeneformamides, diazeneacetamides, bis(diazenefonmamides), bis(diazeneacetamides), poly(diazeneformamides), and poly(diazeneacetamides) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformamide, diazeneacetamide, phenyldiazeneformamide, diphenyldiazeneformamide, phenyldiazeneacetamide, and diphenyldiazeneacetamide.

N—O Valence Stabilizer #30: Examples of diazeneformic acids, diazeneacetic acids, bis(diazeneformic acids), bis(diazeneacetic acids), poly(diazeneformic acids), poly(diazeneacetic acids) and derivatives thereof (N—O Bidentates, N—O Tetradentates, N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazeneformic acid, diazeneacetic acid, phenyldiazeneformic acid, diphenyldiazeneformic acid, phenyldiazeneacetic acid, and diphenyldiazeneacetic acid.

N—O Valence Stabilizer #31: Examples of diazenefonmaldehydes, diazeneacetaldehydes, bis(diazeneformaldehydes), bis(diazeneacetaldehydes), poly(diazenefonmaldehydes), and poly(diazeneacctaldehydes) (N—O Bidentates, N—O Tetradentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenefonmaldehyde, diazeneacetaldehyde, phenyldiazeneformaldehyde, diphenyldiazeneformaldehyde, phenyldiazeneacetaldehyde, and diphenyldiazeneacetaldehyde.

N—O Valence Stabilizer #32: Examples of diazenediformamides, diazenediacetamides, bis(diazenediformamides), bis(diazenediacetamides), poly(diazenedifonmamides), and poly(diazenediacetamides) (N—O Tridentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenedifonmamide, diazenediacetamide, diphenydiazenediformamide, tetraphenyldiazenediformamide, diphenyldiazenediacetamide, and tetraphenyldiazenediacetamide.

N—O Valence Stabilizer #33: Examples of diazenediformic acids, diazenediacetic acids, bis(diazenediformic acids), bis(diazenediacetic acids), poly(diazenediformic acids), poly(diazenediacetic acids) and derivatives thereof (N—O Tridentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazenediformic acid, diazenediacetic acid, phenyldiazenediformic acid, diphenyldiazenediformic acid, phenyldiazenediacetic acid, and diphenyldiazenediacetic acid.

N—O Valence Stabilizer #34: Examples of diazenedifonmaldehydes, diazenediacetaldehydes, bis(diazenediformaldehydes), bis(diazenediacetaldehydes), poly(diazenedifonmaldehydes), and poly(diazenediacetaldehydes) (N—O Tridentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: diazenedifonmaldehyde, diazenediacetaldehyde, diphenyldiazenediformaldehyde, and diphenyldiazenediacetaldehyde.

N—O Valence Stabilizer #35: Examples of ortho-hydroxy (or -carboxy) substituted formazans, bis(o-hydroxy or -carboxy substituted formazans), and poly(o-hydroxy or carboxy substituted formazans) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1-(2-hydroxyphenyl)-3,5-diphenylformazan; 1-(2-methoxyphenyl)-3,5-diphenylformazan; 1,5-bis(2-hydroxyphenyl)-3-phenylformazan; and 5-bis(2-methoxyphenyl)-3-phenylformazan.

N—O Valence Stabilizer #36: Examples of ortho-hydroxy (or -carboxy) substituted azines (including ketazines), bis(o-hydroxy or carboxy substituted azines), and poly(o-hydroxy or carboxy substituted azines) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-hydroxy-1-benzalazine; 2-hydroxy-1-naphthalazine; and 2-hydroxy-1-cyclohexanonazine.

N—O Valence Stabilizer #37: Examples of Schiff Bases with one Imine (C═N) Group and with ortho- or alpha-or beta-hydroxy or carboxy or carbonyl substitution (N—O Bidentates, N—O Tridentates, N—O Tetradentates, N—O Pentadentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-(Salicylaldehydo)isopropylamine; N-(2-Furfuralo)isopropylamine; N-(2-Acetylfurano)isopropylamine; N-(2-H ydroxyacetophenono)isopropylamine; N-(Pyridoxalo)isopropylamine; N-(Salicylaldehydo)cyclohexylamine; N-(2-Furfuralo)cyclohexylamine; N-(2-Acetyl furano)cyclohexylamine; N-(2-Hydroxyacetophenono)cyclohexylamine; N-(Pyridoxalo)cyclohexylamine; N-(Salicylaldehydo)aniline; N-(2-Furfuralo)aniline (Stenhauz salt); N-(2-Acetylfurano)aniline; N-(2-Hydroxyacetophenono)aniline; N-(Pyridoxalo)aniline; N-(Salicylaldehydo)aminonorbornane; N-(2-Furfuralo)aminonorbornane; N-(2-Acetylfurano)aminonorbornane; N-(2-Hydroxyacetophenono)aminonorbornane; N-(Pyridoxalo)aminonorbornane; (Salicylaldehydo)anisidine; 2-salicylideneiminobenzothiazole; (Salicylaldehydo)sulfamethazine; and N′-histidine-3-methoxysalicylidenimine (V-his); N-(o-carboxybenzaldehydo)-2-aminophenol; N-(salicylaldehydo)isatin; N-(2-furfuralo)isatin; N-(2-acetylfurano)isatin; N-(pyridoxalo)isatin; N-(2-hydroxyacetophenono)isatin; hydrofuramide; 2-furancarboxaldehyde phenylhydrazone; 2-furancarboxaldehyde 2-pyridyl hydrazone; salicylaldehyde phenylhydrazone; and salicylaldehyde 2-pyridyl hydrazone. Also includes hydrazones with ortho-O substitution.

N—O Valence Stabilizer #38: Examples of Schiff Bases with two Imine (C═N) Groups and with ortho- or alpha- or beta-hydroxy or carboxy or carbonyl substitution (N—O Tridentates, N—O Tetradentates, N—O Pentadentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-(2,5-Furandicarboxaldehydo)diisopropylamine; N,N′-(2,5-Furandicarboxaldehydo)dicyclohexylamine; N,N′-(2,5-Furandicarboxaldehydo)dianiline; N,N′-(2,5-Furandicarboxaldehydo)di-aminonorbornane; N,N′-(o-Hydroxyphthalicdialdehydo)diisopropylamine; N,N′-(o-Hydroxyphthalicdialdehydo)dicyclohexylamine; N,N′-(o-Hydroxyphthalicdialdehydo)dianiline; N,N′-(o-Hydroxyphthalicdialdehydo)di-aminonorbornane; N,N′-(o-Hydroxyformylcamphoro)diisopropylamine; N,N′-(o-Hydroxyformylcamphoro)dicyclohexylamine; N,N′-(o-Hydroxyformylcamphoro)dianiline; N,N′-(o-Hydroxyformylcamphoro)di-aminonorbornane; N,N′-(o-Hydroxydiacetylbenzeno)diisopropylamine; N,N′-(o-Hydroxydiacetylbenzeno)dicyclohexylamine; N,N′-(o-Hydroxydiacetylbenzeno)dianiline; N,N′-(o-Hydroxydiacetylbenzeno)di-aminonorbornane; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)diisopropylamine; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)dicyclohexylamine; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)dianiline; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)di-aminonorbornane; N,N′-(2,5-Diacetyl furano)diisopropyl amine; N,N′-(2,5-Diacetylfurano)dicyclohexylamine; N,N′-(2,5-Diacetylfurano)dianiline; N,N′-(2,5-Diacetylfurano)di-aminonorbornane; N,N′-(Salicylaldehydo)ethylenediamine; N,N′-(o-Hydroxynaphthaldehydo)ethylenediamine; N,N′-(o-Hydroxyacetophenono)ethylenediamine; N,N′-(Salicylaldehydo)trimethylenediamine; N,N′-(o-Hydroxynaphthaldehydo)trimethylenediamine; N,N′-(o-Hydroxyacetophenono)trimethylenediamine; N,N′-(Salicylaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Hydroxynapbthaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Hydroxyacetophenono)cyclohexane-1,2-diamine; N,N′-(Salicylaldehydo) 1,2-diaminobenzene; N,N′-(o-Hydroxynaphthaldehydo)-1,2-diaminobenzene; N,N′-(o-Hydroxyacetophenono)-1,2-diaminobenzene; N,N′-bis(salicylaldehydo)-1,12-diaminododecane (Saldn); N,N′-bis(3-methoxysalicylaldehydo)-o-phenyldiamine; N,N′-bis(3,4-difluorobenzaldehydo)-4,4′-benzidine; and N,N′-phenylenebis(3-methoxysalicylidenimine) (V-ph-V). Also includes hydrazones with ortho-O substitution.

N—O Valence Stabilizer #39: Examples of Schiff Bases with three Imine (C═N) Groups and with ortho- or alpha- or beta-hydroxy or carboxy or carbonyl substitution (N—O Tetradentates, N—O Pentadentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′,N″-(Salicylaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(o-Hydroxynaphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(o-Hydroxyacetophenono)tris(2=aminoethyl)amine. Also includes hydrazones with ortho-O substitution.

N—O Valence Stabilizer #40: Examples of silylaminoalcohols (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: silatranes.

N—O Valence Stabilizer #41: Examples of hydroxyalkyl imines (imino alcohols) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-hydroxycyclohexylimine; 3-hydroxy-2-iminonorbornane; 2,2′-diiminodicyclohexyl ether; oxamide; 3-imino-1,5-pentanedialdehyde; iminodiacetic acid; and iminodipropionic acid.

N—O Valence Stabilizer #42: Examples of hydroxyaryl amines and hydroxyaryl imines (NO Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminophenol; 2-aminobenzoic acid (anthranilic acid); 2-aminoanisole; o-phenetidine; o-anisidine; 2-hydroxymethyl)-alpha-aminotoluene; 1-amino-2-naphthol; 2-amino-1-naphthol; 2,2′-di(aminomethyl)diphenylketone; isophoronediamine; tris-2,4,6-dimethylaminomethyl phenol; di(2-amino)phenyl ether; 1,3-di(2-amino)phenyl-2-hydroxypropane; 1,3-di(3-amino)phenyl-2-hydroxypropane; 1,3-di(2-hydroxy)phenyl-2-aminopropane; 1,3-di(3-hydroxy)phenyl-2-aminopropane; 2,2′-dihydroxyiminodibenzyl; 2,2′-iminodibenzoic acid; 2,2′-dihydroxyiminostilbene; poly(o-phenetidine); poly(o-aminophenol); poly(o-anisidine); and 3-(anilino)propionamide.

N—O Valence Stabilizer #43: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-hydroxypyrrole; 2-(methylhydroxy)methylpyrrole; 2,5-(hydroxymethyl)pyrrole; 2,5-(methylhydroxymethyl)pyrrol; imidazoline-2-one (2-hydroxyimidazole); 2-hydroxythiazoline; 2-hydroxybenzimidazole; 2-hydroxybenzothiazole; 2-hydroxybenzoxazole; 2-hydantoin; di-2-pyridylglyoxal (2,2′-pyridil); bis((1-pyrazolyl)methane)ether; bis(2-(1-pyrazolyl)ethane)ether; bis(benzimidazolylmethane)ether; bis(benzimidazolylethane)ether; tris(imidazolyl)methanol; tris(imidazolylmethane)methanol; N-hydroxymethyl-N,N-(benzimidazolylmethane)amine; N-(2-hydroxyethyl)-N,N-(benzimidazolylmethane)amine; N,N′-di(benzimidazolylmethane)-1,3-diamino-2-hydroxypropane; N,N,N′,N′-tetrakis(benzimidazolylmethane)-1,3-diamino-2-hydroxypropane; bis(N,N-((4-imidazolyl)methane)2-aminoethane)ether; 4-carboxybenzotriazole; antipyrine; 4-aminoantipyrine (aap); hydantoin; aminoalkylhydantoins; 2,5-oxazolidinedione; benzyldibenzoyltriazole (bdbt); 5-hydroxymethylimidazole; dicarboxyalkylbenzotriazoles; bis(hydroxyphenyl)aminotriazoles; pyrrole-2-carboxaldehyde; (oxopyrrolidinylalkyl)triazoles; alkoxybenzotriazoles; aryloxybenzotriazoles; 3-salicylamido-4,5-dihydro-1,2,4-triazole; 5-(alkoxy)benzotriazole; (polyoxyalkylene)oxazolidines; 1-(dialkylaminomethyl)-5-carboxyalkylbenzotriazole; 1-(2-hydroxyethyl)imidazoline; 1-acetoxyimidazole; 1-acetylimidazole; benzotriazolecarboxylic acid; poly(oxyalkylated)pyrazoles; poly(oxyalkylated)thiadiazoles; 1,2,4-triazole-3-carboxylic acid; 5-hydroxypyrazole; 3-phenyl-1,2,4-triazol-5-one (ptr); 1-acetylbenzimidazole; 1-[(acetoxy)ethyl]benzimidazole; creatinine; indole-2-carboxylic acid; pyrrole-2-carboxylic acid; imidazole-2-carboxylic acid; pyrazole-2-carboxylic acid; and 1,1′-oxalyldiimidazole.

N—O Valence Stabilizer #44: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-aminomethyl-3-pyridinemethanol (including pyridoxamine); 2-hydroxypyridine; 2-(methylhydroxy)methylpyridine; 2-(2-(methylhydroxy)ethyl)pyridine; 2,6-(hydroxymethyl)pyridine; 2,6-(methylhydroxymethyl)pyridine; 2-hydroxypyrimidine; 2-dihydroxymethylpyrimidine; 2-hydroxyquinoline; 8-hydroxyquinoline (oxine); 8-methylhydroxyquinoline; 2-hydroxyquinazoline; orotic acid (1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidinecarboxylic acid) (6-uracilcarboxylic acid); 1-methylpyrimidine-2-one; uracil; 6-hydroxypurine; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminomethane)ether; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminoetbane)ether; quinazol-4-one; quinazol-2-one; 5-azathymine; 2-hydroxybenzimidazole (2-hbz); guanine; 1,3,5-triazin-6-one; 6-hydroxy-1,3,5-triazine; 4,6-dihydroxy-1,3,5-triazine; triazine carboxylic acids; 2,3-dihydroxypyridine; thiomorpholin-3-one; hydroxytetrahydropyrimidines; 2-piperazinones; 2-piperidinones; dilituric acid; actinoquinol; caffeine; citrazinic acid; picolinic acid; 2-quinolol; 2,6-dimethoxypyridine; quinoxaline-2-carboxylic acid; flucytosine; hypoxanthine; hexamethylolmelamine; hydroorotic acid; isoorotic acid; xantbine; leucopterin; nitroorotic acid; 8-azaguanine; and cyanuric acid.

N—O Valence Stabilizer #45: Examples of five-membered heterocyclic rings containing one or two oxygen atoms at least one additional nitrogen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminofuran; 2,5-diaminofuran; 2-aminomethylfuran; 2,5-di(aminomethyl)furan; 2-aminobenzofuran; and 2-amino-1,3-dioxolane.

N—O Valence Stabilizer #46: Examples of six-membered heterocyclic rings containing one or two oxygen atoms at least one additional nitrogen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminopyran; 2,6-diaminopyran; 2-aminomethylpyran; 2,6-di(aminomethyl)pyran; and 2-aminobenzopyran.

N—O Valence Stabilizer #47: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site in a separate ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-furan)pyrrole; 2,5-di(2-furan)pyrrole; 2-(2-pyran)pyrrole; 2,5-di(2-pyran)pyrrole; 2,5-di(2-pyrrole)furan; and 2,6-di(2-pyrrole)pyran.

N—O Valence Stabilizer #48: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site in a separate ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-furan)pyridine; 2,6-di(2-furan)pyridine; 2-(2-pyran)pyridine; 2,6-di(2-pyran)pyridine; 2,5-di(2-pyridyl)furan; 2,6-di(2-pyridyl)pyran; and drometrizole.

N—O Valence Stabilizer #49: Examples of two-, three-, four-, six-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or oxygen (usually hydroxy, carboxy, or carbonyl groups) and are not contained in component heterocyclic rings (N—O Bidentates, N-O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azaoxacyclobutane ([4]aneNO); azaoxacyclopentane ([5]aneNO); azaoxacyclohexane ([6]aneNO); azaoxacycloheptane ([7]aneNO); azaoxacyclooctane ([8]aneNO); azaoxacyclobutene ([4]eneNO); azaoxacyclopentene ([5]eneNO); azaoxacyclohexene ([6]eneNO); azaoxacycloheptene ([7]eneNO); azaoxacyclooctene ([8]eneNO); azaoxacyclobutadiene ([4]dieneNO); azaoxacyclopentadiene ([5]dieneNO); azaoxacyclohexadiene ([6]dieneNO); azaoxacycloheptadiene ([7]dieneNO); azaoxacyclooctadiene ([8]dieneNO); diazaoxacyclohexane ([6]aneON₂); diazaoxacycloheptane ([7]aneON₂); diazaoxacyclooctane ([8]aneON₂); diazaoxacyclononane ([9]aneON₂); diazaoxacyclodecane ([10]aneON₂); diazaoxacycloundecane ([11]aneON₂); diazaoxacyclododecane ([12]aneON₂); diazaoxacyclohexene ([6]eneON₂); diazaoxacycloheptene ([7]eneON₂); diazaoxacyclooctene ([8]eneON₂); diazaoxacyclononene ([9]eneON₂); diazaoxacyclodecene ([10]eneON₂); diazaoxacycloundecene ([11]eneON₂); diazaoxacyclododecene ([12]eneON₂); diazadioxacyclooctane ([8]aneO₂N₂); diazadioxacyclononane ([9]aneO₂N₂); diazadioxacyclodecane ([10]aneO₂N₂); diazadioxacycloundecane ([11]aneO₂N₂); diazadioxacyclododecane ([12]aneO₂N₂); diazadioxacyclotridecane ([13]aneO₂N₂); diazadioxacyclotetradecane ([14]aneO₂N₂); diazadioxacyclopentadecane ([15]aneO₂N₂); diazadioxacyclohexadecane ([16]aneO₂N₂); diazadioxacycloheptadecane ([17]aneO₂N₂); diazadioxacyclooctadecane ([18]aneO₂N₂); diazadioxacyclononadecane ([19]aneON₂); diazadioxacycloeicosane ([20]aneO₂N₂); diazadioxacyclooctadiene ([8]dieneO₂N₂); diazadioxacyclononadiene ([9]dieneO₂N₂); diazadioxacyclodecadiene ([10]dieneO₂N₂); diazadioxacycloundecadiene ([11]dieneO₂N₂); diazadioxacyclododecadiene ([12]dieneO₂N₂); diazadioxacyclotridecadiene ([13]dieneO₂N₂); diazadioxacyclotetradecadiene ([14]dieneO₂N₂); diazadioxacyclopentadecadiene ([15]dieneO₂N₂); diazadioxacyclohexadecadiene ([16]dieneO₂N₂); diazadioxacycloheptadecadiene ([17]dieneO₂N₂); diazadioxacyclooctadecadiene ([18]dieneO₂N₂); diazadioxacyclononadecadiene ([19]dieneO₂N₂); and diazadioxacycloeicosadiene ([20]dieneO₂N₂).

N—O Valence Stabilizer #50: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in component heterocyclic rings (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dipyrandipyridines; difurandipyrroles; tripyrantripyridines; trifurantripyrroles; tetrapyrantetrapyridines; and tetrafurantetrapyrroles.

N—O Valence Stabilizer #51: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in a combination of heterocyclic rings and amine, imine, hydroxy, carboxy, or carbonyl groups (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azaoxatetraphyrins; diazadioxatetraphyrins; azaoxahexaphyrins; diazadioxahexaphyrins; and triazatrioxahexaphyrins.

S—O Valence Stabilizer #1: Examples of 1,3-monothioketones (monothio-beta-ketonates), 1,3,5-monothioketones, 1,3,5-dithioketones, bis(1,3-monothioketones), and poly(1,3-monothioketones) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexafluoropenta-2-thione-4-ketone; 1,3-diphenyl-1,3-propana-1-thione-3-ketone; benzoylthiopinacolone; cyclohexoylthiocyclohexoylmethane; diphenylpentanedithionate; tetramethylnonanedithionate; hexafluoroheptanedithionate; trifluoroheptanedithionate; 1-(2-thienyl)-butan-1-thione-3-ketone, 1-(2-naphthyl)-butan-1-thione-3-ketone, and trifluoroacetylthiocamphor.

S—O Valence Stabilizer #2: Examples of thiomalonamides (thiomalonodiamides), bis(thiomalonamides), and polythiomalonamides (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiomalonamide, N-phenylthiomalonamide, N-benzylthiomalonamide, N-pentafluorophenylthiomalonamide, N-cyclohexylthiomalonamide, N-norbornylthiomalonamide, N,N′-diphenylthiomalonamide, N,N′-dibenzylthiomalonamide, N,N′-dipentafluorophenylthiomalonamide, N,N′-dicyclohexylthiomalonamide, and N,N′-norbornylthiomalonamide.

S—O Valence Stabilizer #3: Examples of 2-thioacylacetamides, 2-acylthioacetamides, bis(2-thioacylacetamides), bis(2acylthioacetamides), poly(2-thioacylacetamides), and poly(2-Acylthioacetamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-acetothioacetamide, 2-thioacetoacetamide, N-phenyl-2-acetothioacetamide, N-pentafluorophenyl-2-acetothioacetamide, N-benzyl-2-acetothioacetamide, N-cyclohexyl-2-acetothioacetamide, N-norbornyl-2-acetothioacetamide, N-phenyl-2-benzothioacetamide, N-pentafluorophenyl-2-pentafluorobenzothioacetamide, and N-cyclohexyl-2-cyclohexothioacetamide.

S—O Valence Stabilizer #4: Examples of dithiodicarbonic diamides, bis(dithiodicarbonic diamides), and poly(dithiodicarbonic diamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodicarbonic diamide; N-phenyldithiodicarbonic diamide; N-pentafluorophenyldithiodicarbonic diamide; N-benzyldithiodicarbonic diamide; N-cyclohexyldithiodicarbonic diamide; N-norbornyldithiodicarbonic diamide; N,N′-diphenyldithiodicarbonic diamide; N,N′-dipentafluorophenyldithiodicarbonic diamide; N,N′-dibenzyldithiodicarbonic diamide; N,N′-dicyclohexyldithiodicarbonic diamide; and N,N′-dinorbornyldithiodicarbonic diamide.

S—O Valence Stabilizer #5: Examples of monothiohypophosphoric acids, bis(monothiohypophosphoric acids), poly(monothiohypophosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiohypophosphoric acid, methylmonothiohypophosphoric acid, isopropylmonothiohypophosphoric acid, tert-butylmonothiohypophosphoric acid, phenylmonothiohypophosphoric acid, pentafluorophenylmonothiohypophosphoric acid, benzylmonothiohypophosphoric acid, cyclohexylmonothiohypophosphoric acid, norbornylmonothiohypophosphoric acid, dimethylmonothiohypophosphoric acid, diisopropylmonothiohypophosphoric acid, di-tert-butylmonothiohypophosphoric acid, diphenylmonothiohypophosphoric acid, di-pentafluorophenylmonothiohypophosphoric acid, dibenzylmonothiohypophosphoric acid, dicyclohexylmonothiohypophosphoric acid, and dinorbornylmonothiohypophosphoric acid.

S—O Valence Stabilizer #6: Examples of monothiohypophosphoramides, bis(monothiohypophosphoramides), and poly(monothiohypophosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiohypophosphoramide, N-methylmonothiohypophosphoramide, N-isopropylmonothiohypophosphoramide, N-tert-butylmonothiohypophosphoramide, N-phenylmonothiohypophosphoramide, N-pentafluorophenylmonothiohypophosphoramide, N-benzylmonothiohypophosphoramide, N-cyclohexylmonothiohypophosphoramide, N-norbornylmonothiohypophosphoramide, N,N′″-dimethylmonothiohypophosphoramide, N,N′″-diisopropylmonothiohypophosphoramide, N,N′″-di-tert-butylmonothiohypophosphoramide, N,N′″-diphenylmonothiohypophosphoramide, N,N′″-di-pentafluorophenylmonothiohypophosphoramide, N,N′″-dibenzylmonothiohypophosphoramide, N,N′″-dicyclohexylmonothiohypophosphoramide, and N,N″-dinorbornylmonothiohypophosphoramide.

S—O Valence Stabilizer #7: Examples of monothioimidodiphosphoric acids, monothiohydrazidodiphosphoric acids, bis(monothioimidodiphosphoric acids), bis(monothiohydrazidodiphosphoric acids), poly(monothioimidodiphosphoric acids), poly(monothiohydrazidodiphosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioimidodiphosphoric acid, methylmonothioimidodiphosphoric acid, isopropylmonothioimidodiphosphoric acid, tert-butylnonothioimidodiphosphoric acid, phenylmonothioimidodiphosphoric acid, pentafluorophenylmonothioimidodiphosphoric acid, benzylmonothioimidodiphosphoric acid, cyclohexylmonothioimidodiphosphoric acid, norbornylmonothioimidodiphosphoric acid, dimethylmonothioimidodiphosphoric acid, diisopropylmonothioimidodiphosphoric acid, di-tert-butylmonothioimidodiphosphoric acid, diphenylmonothioimidodiphosphoric acid, di-pentafluorophenylmonothioimidodiphosphoric acid, dibenzylmonothioimidodiphosphoric acid, dicyclohexylmonothioimidodiphosphoric acid, and dinorbornylmonothioimidodiphosphoric acid.

S—O Valence Stabilizer #8: Examples of monothioimidodiphosphoramides, monothiohydrazidodiphosphoramides, bis(monothioimidodiphosphoramides), bis(monothiohydrazidodiphosphoramides), poly(monothioimidodiphosphoramides), and poly(monothiohydrazidodiphosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioimidodiphosphoramide, N-methylmonothioimidodiphosphoramide, N-isopropylmonothioimidodiphosphoramide, N-tert-butylmonothioimidodiphosphoramide, N-phenylmonothioimidodiphosphoramide, N-pentafluorophenylmonothioimidodiphosphoramide, N-benzylmonothioimidodiphosphoramide, N-cyclohexylmonothioimidodiphosphoramide, N-norbornylmonothioimidodiphosphoramide, N,N′″-dimethylmonothioimidodiphosphoramide, N,N′″-diisopropylmonothioimidodiphosphoramide, N,N′″-di-tert-butylmonothioimidodiphosphoramide, N,N′″-diphenylmonothioimidodiphosphoramide, N,N′″-di-pentafluorophenylmonothioimidodiphosphoramide, N,N′″-dibenzylmonothioimidodiphosphoramide, N,N′″-dicyclohexylmonothioimidodiphosphoramide, and N,N′″-dinorbornylmonothioimidodiphosphoramide.

S—O Valence Stabilizer #9: Examples of monothiodiphosphoramides, bis(monothiodiphosphoramides), and poly(monothiodiphosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiodiphosphoramide, N-methylmonothiodipbosphoramide, N-isopropylmonothiodiphosphoramide, N-tert-butylmonothiodiphosphoramide, N-phenylmonothiodiphosphoramide, N-pentafluorophenylmonothiodiphosphoramide, N-benzylmonothiodiphosphoramide, N-cyclohexylmonothiodiphosphoramide, N-norbornylmonothiodiphosphoramide, N,N′″-dimethylmonothiodiphosphoramide, N,N′″-diisopropylmonotbiodiphosphoramide, N,N′″-di-tert-butylmonothiodiphosphoramide, N,N′″-diphenylmonothiodiphosphoramide, N,N′″-di-pentafluorophenylmonothiodiphosphoramide, N,N′″-dibenzylmonothiodiphosphoramide, N,N′″-dicyclohexylmonothiodiphosphoramide, and N,N′″-dinorbornylmonothiodiphosphoramide.

S—O Valence Stabilizer #10: Examples of monothiodiphosphoric acids, bis(monotbiodiphosphoric acids), poly(monothiodiphosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiodiphosphoric acid, methylmonothiodiphosphoric acid, isopropylmonothiodiphosphoric acid, tert-butylmonothiodiphosphoric acid, phenylmonothiodiphosphoric acid, pentafluorophenylmonothiodiphosphoric acid, benzylmonothiodiphosphoric acid, cyclohexylmonothiodiphosphoric acid, norbornylmonothiodiphosphoric acid, dimethylmonothiodiphosphoric acid, diisopropylmonothiodiphosphoric acid, di-tert-butylmonothiodiphosphoric acid, diphenylmonothiodiphosphoric acid, di-pentafluorophenylmonothiodiphosphoric acid, dibenzylmonothiodiphosphoric acid, dicyclohexylmonothiodiphospboric acid, and dinorbornylmonothiodiphosphoric acid.

S—O Valence Stabilizer #11: Examples of monothiocarbamates, bis(monothiocarbamates), and poly(monothiocarbamates) (including N-hydroxymonothiocarbamates and N-mercaptomonothiocarbamates) (S—O Bidentates, S—O Tridentates, and S—O Tetradentates) that rmeet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dimethylmonothiocarbamate (dmmtc); di(trifluorodimethyl)monothiocarbamate; diethylmonothiocarbamate (demtc); dipropylmonothiocarbamate; diisopropylmonothiocarbamate; dibutylmonothiocarbamate; ditertbutylmonothiocarbamate; dicyanamidomonothiocarbamate; diphenylmonothiocarbamate; di(pentafluorophenyl)monothiocarbamate; dibenzylmonothiocarbamate; dinaphthylmonothiocarbamate; dicyclohexylmonothiocarbamate; dinorbornylmonothiocarbamate; diadamantylmonothiocarbamate; pyrrolidinomonothiocarbamate (pyrmtc); piperidinomonothiocarbamate (pipmtc); morpholinomonothiocarbamate (mormtc); thiamorpholinomonothiocarbamate; 3-pyrrolinomonothiocarbamate; pyrrolomonothiocarbamate; oxazolomonothiocarbamate; isoxazolomonothiocarbamate; thiazolomonothiocarbamate; isothiazolomonothiocarbamate; indolomonothiocarbamate; carbazolomonothiocarbamate; pyrazolinomonothiocarbamate; imidazolinomonothiocarbamate; pyrazolomonothiocarbamate; imidazolomonothiocarbamate; indazolomonothiocarbamate; and triazolomonothiocarbamate.

Miscellaneous Valence Stabilizer #1: Examples of hydroxo and oxo functionalities that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: water (H₂O); dioxygen (O₂); oxide (O² ⁻); hydroxide (OH⁻); peroxo groups (O₂ ²⁻); and superoxo groups (O₂ ⁻).

As with the inorganic valence stabilizers, crosses between two or more organic stabilizers can be used. For example, in some instances it may be desirable to form a valence stabilizer out of a nitrogen-containing heterocyclic and an amine ligand. During the synthesis process, both of these materials will complex with the MnIII or MnIV ion to produce a mixed nitrogen heterocyclic/amine valence stabilizer compound from the pigment solution.

3c) Narrow Band Inorganic Valence Stabilizers

Additional valence stabilizers can be used in conjunction with the MnIII and MnIV ions for corrosion protection. However, these less typical stabilizers suffer from disadvantages that make their selection over the previously mentioned wide band valence stabilizers less desirable. For this reason, we term them “narrow band” valence stabilizers because of their limited applications. Narrow band stabilizers exhibit some limitation in their use when compared to wide band stabilizers. Narrow band inorganic stabilizers may be toxic or may complex MnII or MnIV only with difficulty. These narrow band stabilizers include, but are not limited to, bismuthates, gennanates, arsenates, and carbonates. For example, valence stabilizers using arsenate are less desirable because their inherent toxicity is very large (greater than PbIV or CrVI), although they may be very effective at inhibiting corrosion when used with MnII. Arsenates could be used as MnIII valence stabilizers in situations where the toxicity of the pigment is not a factor in its use.

Modifications of wide band inorganic valence stabilizers can result in a complex with reduced corrosion inhibition. The central cavity of the heteropolymetallates can contain ions in addition to the desired MnIII or MnIV ion. For example, the use of silicomolybdates, phosphomolybdates, silicotungstates, and phosphotungstates is possible. In these MnIII- or MnIV-valence stabilizer complexes, Si ⁺⁴or P⁺⁵ions also occupy the central cavity of the complex with the MnIII or MnIV ion. The inclusion of additional ions in the central cavity reduces the stability of the complex, and thereby leads to lower corrosion protection. Nonetheless, these complexes also demonstrate some corrosion inhibiting activity. The additional ions that can be included within the central cavity of the heteropolymetallates described above depend upon the size of the central cavity, which in turn depends upon the specific chemistry exhibited by an inorganic valence stabilizer (e.g., molybdate, tungstate, periodate, etc.) In general, these additional ions must also be small so as to ensure the stability of the formed MnIII- or MnIV-valence stabilized complex. Examples of small additional ions include, but are not limited to: B⁺³, Al⁺³, Si⁺⁴, P⁺⁵, Ti⁺⁴, V⁺⁵, V⁺⁴, Cr⁺⁶, Cr⁺³, Mn⁺², Fe⁺³, Fe⁺², CO⁺³, CO⁺², Ni⁺², N⁺³, Ni⁺⁴, CU⁺², Cu⁺³, Zn⁺², Ga⁺³, Ge⁺⁴, AS⁺⁵, As⁺³, Zr⁺⁴, and Ce⁺⁴.

Water-soluble precursors for these materials are desirable. Typically, the free acids (e.g., silicomolybdic acid, phosphotungstic acid, borotungstic acid, etc.) offer the most water-soluble precursors for these materials.

3d) Narrow Band Organic Valence Stabilizers

Narrow band organic valence:stabilizers include those general classes of chemical compounds that result in MnIII- or MnIV-valence stabilizer compounds that are either less stable, more soluble in water, or more toxic than the wide band organic stabilizers.

TABLE 5


Narrow Band Organic Valence Stabilizers for the Mn⁺³and Mn⁺⁴Ions

General Structural Name
(Type of Organic)	Structural Representation

N Valence Stabilizer #1:	Macrocyclic ligands containing five, seven, or
Five-, Seven-, or Nine-Membered	nine nitrogen binding sites to valence stabilize
Macrocyclics, Macrobicyclics, and	the central metal ion. Can include other
Macropolycyclics (including Catapinands,	hydrocarbon or ring systems bound to this
Cryptands, Cyclidenes, and Sepulchrates)	macrocyclic ligand, but they do not coordinate
wherein all Binding Sites are composed of	with the stabilized, high valence metal ion. This
Nitrogen (usually amine or imine groups)	ligand and/or attached, uncoordinating
and are not contained in Component	hydrocarbons/rings may or may not have
Heterocyclic Rings (N—N Tridentates, N—N	halogen or polarizing or water-
Tetradentates, and N—N Hexadentates)	insolubilizing/solubilizing groups attached.
N Valence Stabilizer #2:	Macrocyclic ligands containing a total of five or
Five-, or Seven-Membered Macrocyclics,	seven five-membered heterocyclic rings
Macrobicyclics, and Macropolycyclics	containing nitrogen binding sites. Can include
(including Catapinands, Cryptands,	other hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Nitrogen	with the stabilized, high valence metal ion. This
and are contained in Component 5-	ligand and/or attached, uncoordinating
Membered Heterocyclic Rings (N—N	hydrocarbon/rings may or may not have halogen
Tridentates, N—N Tetradentates, or N—N	or polarizing or water-insolubilizing groups
Hexadentates)	attached.
N Valence Stabilizer #3:	Macrocyclic ligands containing at least one 5-
Five-, Seven-, or Nine-Membered	membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and	heterocyclic rings provide nitrogen binding sites
Macropolycyclics (including Catapinands,	to valence stabilize the central metal ion. Other
Cryptands, Cyclidenes, and Sepulchrates)	amine or imine binding sites can also be
wherein all Binding Sites are composed of	included in the macrocyclic ligand, so long as
Nitrogen and are contained in a	the total number of binding sites is five, seven,
Combination of 5-Membered Heterocyclic	or nine. Can include other hydrocarbon/ring
Rings and Amine or Imine Groups (N—N	systems bound to this macrocyclic ligand, but
Tridentates, N—N Tetradentates, or N—N	they do not coordinate with the stabilized, high
Hexadentates)	valence metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
N Valence Stabilizer #4:	Macrocyclic ligands containing a total of five or
Five- or Seven-Membered Macrocyclics,	seven six-membered heterocyclic rings
Macrobicyclics, and Macropolycyclics	containing nitrogen binding sites. Can include
(including Catapinands, Cryptands,	other hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Nitrogen	with the stabilized, high valence metal ion. This
and are contained in Component 6-	ligand and/or attached, uncoordinating
Membered Heterocyclic Rings (N—N	hydrocarbon/rings may or may not have halogen
Tridentates, N—N Tetradentates, or N—N	or polarizing or water-insolubilizing groups
Hexadentates)	attached.
N Valence Stabilizer #5:	Macrocyclic ligands containing at least one 6-
Five-, Seven-, or Nine-Membered	membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and	heterocyclic rings provide nitrogen binding sites
Macropolycyclics (including Catapinands,	to valence stabilize the central metal ion. Other
Cryptands, Cyclidenes, and Sepulchrates)	amine or imine binding sites can also be
wherein all Binding Sites are composed of	included in the macrocyclic ligand, so long as
Nitrogen and are contained in a	the total number of binding sites is five, seven,
Combination of 6-Membered Heterocyclic	or nine. Can include other hydrocarbon/ring
Rings and Amine or Imine Groups (N—N	systems bound to this macrocyclic ligand, but
Tridentates, N—N Tetradentates, or N—N	they do not coordinate with the stabilized, high
Hexadentates)	valence metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
N Valence Stabilizer #6:	N(SiR₃)₃, R′N(SiR₃)₂, or R′R″N(SiR₃) for
Silylamines and Silazanes, including	silylamines; and [RR″Si—NR′]_x(x = 1-10) for
Macrocyclic Derivatives, wherein at least	silazanes where R, R′, and R″ represents H or
one Nitrogen Atom is a Binding Site (N	any organic functional group wherein the
Monodentates, N—N Bidentates, N—N	number of carbon atoms ranges from 0 to 35,
Tridentates, N—N Tetradentates, and N—N	optionally having halogen or polarizing or
Hexadentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding
	N, P, As, O, S, or Se atoms.
N Valence Stabilizer #7:	RR′—N—C(═NH)NR″R″′, where R, R′, R″, and
Guanidines, Diguanidines, and	R″′ represent H or any organic functional group
Polyguanidines (N—N Bidentates, N—N	wherein the number of carbon atoms ranges
Tridentates, N—N Tetradentates, and N—N	from 0 to 40, optionally having halogen or
Hexadentates)	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N Valence Stabilizer #8:	RR′—N—P(═N)—N—R″R″′, where R, R′, R″, and
Phosphonitrile Amides, and	R″′ represent H or any organic functional group
Bis(phosphonitrile amides) (N—N	wherein the number of carbon atoms ranges
Bidentates, N—N Tetradentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N Valence Stabilizer #9:	(NH═)PR″″(—NRR′)(—NR″R″′), where R, R′,
Phosphonimidic Diamides,	R″, R″′, and R″″ represent H or any organic
Bis(Phosphonimidic Diamides), and	functional group wherein the number of carbon
Poly(Phosphonimidic Diamides) (N—N	atoms ranges from 0 to 40, optionally having
Bidentates, N—N Tetradentates)	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N Valence Stabilizer #10:	(NH═)PR″′(—NRR′)(—OR″) for
Phosphonamidimidic Acid,	phosphonamidimidic acid and (NH═)PR″′(—
Phosphonamidimidothioic Acid,	NRR′)(—SR″) for phosphonamidimidothioic
Bis(Phosphonamidimidic Acid),	acid, where R, R′, R″, and R″′ represent H or
Bis(Phosphonamidimidothioic Acid),	any organic functional group wherein the
Poly(Phosphonamidimidic Acid),	number of carbon atoms ranges from 0 to 40,
Poly(Phosphonamidimidothioic Acid), and	optionally having halogen or polarizing or
derivatives thereof (N—N Bidentates, and N—	water-insolubilizing/solubilizing groups
N Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N Valence Stabilizer #11:	C₅H₅N—CR═NR′, where C₅H₅N is a pyridine
Pyridinaldimines, Bis(pyridinaldimines),	derivative, R is typically an aromatic constituent
and Poly(pyridinaldimines) (N—N	(i.e. —C₆H₅), and R′ represents H or any organic
Bidentates, N—N Tridentates, and N—N	functional group wherein the number of carbon
Tetradentates)	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N Valence Stabilizer #12:	R—NH—N═R′, where R and R′ represent H or
Hydrazones, Bis(hydrazones), and	any organic functional group wherein the
Poly(hydrazones) (N Monodentates, N—N	number of carbon atoms ranges from 0 to 40,
Bidentates, N—N Tridentates, and N—N	optionally having halogen or polarizing or
Tetradentates)	water-insolubilizing/solubilizing groups
	attached. (Either R or R′ is typically an aryl
	group.) Ligand can also contain nonbinding N,
	O, S, or P atoms.
N Valence Stabilizer #13:	R—N═N—R′ for azo compounds, R—N═N—NH—R′
Azo compounds including triazenes without	for triazenes, where R, and R′ represent H or
chelate substitution at the ortho- (for aryl)	any organic functional group wherein the
or alpha- or beta- (for alkyl) positions,	number of carbon atoms ranges from 0 to 40,
Bis(azo compounds), or Poly(azo	optionally having halogen or polarizing or
compounds) (N Monodentates, N—N	water-insolubilizing/solubilizing groups
Bidentates, or N—N—N Tridentates)	attached. (Not including ortho- chelate
	substituted aryl azo compounds, and alpha- or
	beta-substituted alkyl azo compounds.) Ligand
	can also contain nonbinding N, O, S, or P
	atoms.
N Valence Stabilizer #14:	R—N═N—CR′═N—NR″R″′, where R, R′, R″, and
Formazans, Bis(formazans), and	R″′ represent H, or any organic-functional
Poly(formazans) without ortho- hydroxy,	group wherein the number of carbon atoms
carboxy, thiol, mercapto, amino, or	ranges from 0 to 40, optionally having halogen
hydrazido substitution (N—N Bidentates, N—	or polarizing or water-
N Tetradentates, and N—N Hexadentates)	insolubilizing/solubilizing groups attached. (Not
	including ortho- hydroxy, carboxy, thiol,
	mercapto, amino, or hydrazido substitution.)
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N Valence Stabilizer #15:	R—CH═N—CHR′—N═CHR″, where R, R′, and R″
Hydramides (N—N Bidentates)	represent H, or any organic functional group
	wherein the number of carbon atoms ranges
	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. (R, R′, and R″ are typically
	aryl derivatives.) Ligand can also contain
	nonbinding N, O, S, or P atoms.
N Valence Stabilizer #16:	RR′C═N—N═CR″R″′ or RR′C═N—NR″R″′ (for
Azines (including ketazines), Bis(azines),	ketazines), where R, R′, R″, and R″′ represent
and Poly(azines) without ortho- hydroxy,	H, or any organic functional group wherein the
carboxy, thiol, mercapto, amino, or	number of carbon atoms ranges from 0 to 40,
hydrazido substitution (N—N Bidentates, N—	optionally having halogen or polarizing or
N Tetradentates, and N—N Hexadentates)	water-insolubilizing/solubilizing groups
	attached. (Not including ortho- hydroxy,
	carboxy, thiol, mercapto, amino, or hydrazido
	substitution.) Ligand can also contain
	nonbinding N, O, S, or P atoms.
N Valence Stabilizer #17:	RR′C═N—R″, where R, R′, and R″ represent H,
Schiff Bases with one Imine (C═N) Group	or any organic functional group wherein the
and without ortho- (for aryl constituents) or	number of carbon atoms ranges from 0 to 40,
alpha- or beta- (for alkyl constituents)	optionally having halogen or polarizing or
hydroxy, carboxy, carbonyl, thiol,	water-insolubilizing/solubilizing groups
mercapto, thiocarbonyl, amino, imino,	attached. (Not including ortho-, alpha-, or beta-
oximo, diazeno, or hydrazido substitution	hydroxy, carboxy, carbonyl, thiol, mercapto,
(N Monodentates)	thiocarbonyl, amino, imino, oximo, diazeno, or
	hydrazido substitution.) Ligand can also
	contain nonbinding N, O, S, or P atoms.
N Valence Stabilizer #18:	Isocyanides, cyanamides, and related ligands
Isocyanide and Cyanamide and related	where the nitrogen atom is directly complexed
ligands (N Monodentates)	to the high valence metal ion.
N Valence Stabilizer #19:	Nitrosyl, nitrite, and related ligands where the
Nitrosyl and Nitrite and related ligands (N	nitrogen atom is bound directly to the high
Monodentates)	valence metal ion.
N Valence Stabilizer #20:	R—CN, R—(CN)₂, R—(CN)_x, etc. where R
Nitriles, Dinitriles, and Polynitriles (N	represents H or any organic functional group
Monodentates, N—N Bidentates, and N—N—N	wherein the number of carbon atoms ranges
Tridentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached.
N Valence Stabilizer #21:	Azide (—N₃) ligands bound directly to the high
Azide ligands (N Monodentates, or N—N	valence metal ion. Also includes organoazide
Bidentates)	derivatives (R—N₃), triazenido compounds (R—
	N₃—R′), phosphonyl azides (R—PO₂H—N₃),
	phosphoryl azides (O—PO₂H—N3), and sulfonyl
	azides (R—SO₂—N₃) where R and R′ represent H
	or any organic functional group wherein the
	number of carbon atoms ranges from 0 to 35,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached
S Valence Stabilizer #1:	SH₂, SHR, SR₂, where R represents H or any
Monothioethers (S Monodentates) wherein	organic functional group wherein the number of
at least one Sulfur Atom is a Binding Site	carbon atoms ranges from 0 to 35, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, O, S,
	or Se atoms.
S Valence Stabilizer #2:	R—S—S—R′, where R and R′ represents H or any
Disulfides (S Monodentates) wherein at	organic functional group wherein the number of
least one Sulfur Atom is a Binding Site	carbon atoms ranges from 0 to 35, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, O, S,
	or Se atoms.
S Valence Stabilizer #3:	R—S—R′—S—R″, where R, R′, and R″ represents H
Dithioethers (S—S Bidentates) wherein at	or any organic functional group wherein the
least one Sulfur Atom is a Binding Site	number of carbon atoms ranges from 0 to 35,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, O, S, or Se atoms.
S Valence Stabilizer #4:	R—S—R′—S—R″—S—R″′, where R, R′, R″, and R″′
Trithioethers (S—S Bidentates or S—S	represents H or any organic functional group
Tridentates) wherein at least one Sulfur	wherein the number of carbon atoms ranges
Atom is a Binding Site	from 0 to 35, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, P, O, S, or Se atoms.
S Valence Stabilizer #5:	R—S—R′—S—R″—S—R″′—S—R″″, where R, R′, R″,
Tetrathioethers (S—S Bidentates, S—S	R″′, and R″″ represents H or any organic
Tridentates, or S—S Bidentates) wherein at	functional group wherein the number of carbon
least one Sulfur Atom is a Binding Site	atoms ranges from 0 to 35, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, O, S,
	or Se atoms.
S Valence Stabilizer #6:	R—S—R′—S—R″—S—R″′—S—R″″—S—R″″′—S—R″″″,
Hexathioethers (S—S Bidentates, S—S	where R, R′, R″, R″′, R″″, R″″′, and R″″″
Tridentates, S—S Tetradentates, or S—S	represents H or any organic functional group
Hexadentates) wherein at least one Sulfur	wherein the number of carbon atoms ranges
Atom is a Binding Site	from 0 to 35, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, P, O, S, or Se atoms.
S Valence Stabilizer #7:	Five membered heterocyclic ring containing one
Five-Membered Heterocyclic Rings	or two sulfur atoms, both of which may function
containing One or Two Sulfur Atoms	as binding sites. Can include other ring systems
wherein at least one Sulfur Atom is a	bound to this heterocyclic ring, but they do not
Binding Site (S Monodentates or S—S	coordinate with the stabilized, high valence
Bidentates)	metal ion. Ring can also contain O, N, P, As, or
	Se atoms. This 5-membered ring and/or
	attached, uncoordinating rings may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S Valence Stabilizer #8:	Six membered heterocyclic ring containing just
Six-Membered Heterocyclic Rings	one or two sulfur atoms, both of which may
containing One or Two Sulfur Atoms	function as binding sites. Can include other
wherein at least one Sulfur Atom is a	ring systems bound to this heterocyclic ring, but
Binding Site (S Monodentates or S—S	they do not coordinate with the stabilized, high
Bidentates)	valence metal ion. Ring can also contain O, N,
	P, As, or Se atoms. This 5-membered ring
	and/or attached, uncoordinating rings may or
	may not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S Valence Stabilizer #9:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at	contains additional sulfur-containing
least one additional Sulfur Atom Binding	substituents (usually thiols or thioethers) that
Site not in a Ring (S Monodentates, S—S	constitute S binding sites. Can include other
Bidentates, S—S Tridentates, S—S	ring systems bound to the heterocyclic ring or to
Tetradentates, or S—S Hexadentates)	the S-containing substituent, but they do not
	coordinate with the stabilized, high valence
	metal ion. Ring(s) can also contain O, N, P, As
	or Se atoms. This 5-membered ring(s) and/or
	attached, uncoordinating rings and/or S-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S Valence Stabilizer #10:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at	contains additional sulfur-containing
least one additional Sulfur Atom Binding	substituents (usually thiols or thioethers) that
Site not in a Ring (S Monodentates, S—S	constitute S binding sites. Can include other
Bidentates, S—S Tridentates, S—S	ring systems bound to the heterocyclic ring or to
Tetradentates, or S—S Hexadentates)	the S-containing substituent, but they do not
	coordinate with the stabilized, high valence
	metal ion. Ring(s) can also contain O, N, P, As
	or Se atoms. This 6-membered ring(s) and/or
	attached, uncoordinating rings and/or S-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S Valence Stabilizer #11:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at	contains additional sulfur-containing rings that
least one additional Sulfur Atom Binding	constitute S binding sites. Can include other
Site in a separate Ring (S Monodentates, S—	ring systems bound to the S-containing
S Bidentates, S—S Tridentates, S—S	heterocyclic rings, but they do not coordinate
Tetradentates, or S—S Hexadentates)	with the stabilized, high valence metal ion.
	Ring(s) can also contain O, N, P, As, or Se
	atoms. This 5-membered ring(s) and/or
	additional S-containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S Valence Stabilizer #12:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at	contains additional sulfur-containing rings that
least one additional Sulfur Atom Binding	constitute S binding sites. Can include other
Site in a separate Ring (S Monodentates, S—	ring systems bound to the S-containing
S Bidentates, S—S Tridentates, S—S	heterocyclic rings, but they do not coordinate
Tetradentates, or S—S Hexadentates)	with the stabilized, high valence metal ion.
	Ring(s) can also contain O, N, P, As, or Se
	atoms. This 6-membered ring(s) and/or
	additional S-containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S Valence Stabilizer #13:	Macrocyclic ligands containing two to ten sulfur
Two-, Three-, Four-, Five-, Six-, Seven-,	binding sites to valence stabilize the central
Eight-, Nine-, and Ten-Membered	metal ion. Can include other hydrocarbon or
Macrocyclics, Macrobicyclics, and	ring systems bound to this macrocyclic ligand,
Macropolycyclics (including Catapinands,	but they do not coordinate with the stabilized,
Cryptands, Cyclidenes, and Sepulchrates)	high valence metal ion. This ligand and/or
wherein all Binding Sites are composed of	attached, uncoordinating hydrocarbons/rings
Sulfur (usually thiol or thioether groups)	may or may not have halogen or polarizing or
and are not contained in Component	water-insolubilizing/solubilizing groups
Heterocyclic Rings (S—S Bidentates, S—S	attached.
Tridentates, S—S Tetradentates, and S—S
Hexadentates)
S Valence Stabilizer #14:	Macrocyclic ligands containing a total of four to
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	ten five-membered heterocyclic rings containing
Ten-Membered Macrocyclics,	sulfur binding sites. Can include other
Macrobicyclics, and Macropolycyclics	hydrocarbon/ring systems bound to this
(including Catapinands, Cryptands,	macrocyclic ligand, but they do not coordinate
Cyclidenes, and Sepulchrates) wherein all	with the stabilized, high valence metal ion. This
Binding Sites are composed of Sulfur and	ligand and/or attached, uncoordinating
are contained in Component 5-Membered	hydrocarbon/rings may or may not have halogen
Heterocyclic Rings (S—S Tridentates, S—S	or polarizing or water-insolubilizing groups
Tetradentates or S—S Hexadentates)	attached.
S Valence Stabilizer #15:	Macrocyclic ligands containing at least one 5-
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	membered heterocyclic ring. These
Ten-Membered Macrocyclics,	heterocyclic rings provide sulfur binding sites to
Macrobicyclics, and Macropolycyclics	valence stabilize the central metal ion. Other
(including Catapinands, Cryptands,	thiol, thioether, or thioketo binding sites can
Cyclidenes, and Sepulchrates) wherein all	also be included in the macrocyclic ligand, so
Binding Sites are composed of Sulfur and	long as the total number of binding sites is four
are contained in a Combination of 5-	to ten. Can include other hydrocarbon/ring
Membered Heterocyclic Rings and Thiol,	systems bound to this macrocyclic ligand, but
Thioether, or Thioketo Groups (S—S	they do not coordinate with the stabilized, high
Tridentates, S—S Tetradentates, or S—S	valence metal ion. This ligand and/or attached,
Hexadentates)	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
S Valence Stabilizer #16:	Macrocyclic ligands containing a total of four to
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	ten six-membered heterocyclic rings containing
Ten-Membered Macrocyclics,	sulfur binding sites. Can include other
Macrobicyclics, and Macropolycyclics	hydrocarbon/ring systems bound to this
(including Catapinands, Cryptands,	macrocyclic ligand, but they do not coordinate
Cyclidenes, and Sepulchrates) wherein all	with the stabilized, high valence metal ion. This
Binding Sites are composed of Sulfur and	ligand and/or attached, uncoordinating
are contained in Component 6-Membered	hydrocarbon/rings may or may not have halogen
Heterocyclic Rings (S—S Tridentates, S—S	or polarizing or water-insolubilizing groups
Tetradentates, or S—S Hexadentates)	attached.
S Valence Stabilizer #17:	Macrocyclic ligands containing at least one 6-
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	membered heterocyclic ring. These
Ten-Membered Macrocyclics,	heterocyclic rings provide sulfur binding sites to
Macrobicyclics, and Macropolycyclics	valence stabilize the central metal ion. Other
(including Catapinands, Cryptands,	thiol, thioether, or thioketo binding sites can
Cyclidenes, and Sepulchrates) wherein all	also be included in the macrocyclic ligand, so
Binding Sites are composed of Sulfur and	long as the total number of binding sites is four
are contained in a Combination of 6-	to ten. Can include other hydrocarbon/ring
Membered Heterocyclic Rings and Thiol,	systems bound to this macrocyclic ligand, but
Thioether, or Thioketo Groups (S—S	they do not coordinate with the stabilized, high
Tridentates, S—S Tetradentates, or S—S	valence metal ion. This ligand and/or attached,
Hexadentates)	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
S Valence Stabilizer #18:	RR′—N—C(═S)—NR″—C(═S)—NR″′R″″ for
Dithiobiurets (Dithioimidodicarbonic	dithiobiurets, and RR′—N—C(═S)—NR″—NH—
Diamides), Dithioisobiurets, Dithiobiureas,	C(═S)—NR″′R″″ for dithiobiureas, where R, R′,
Trithiotriurets, Trithiotriureas,	R″, R″′, and R″″ represent H, NH₂, or any
Bis(dithiobiurets), Bis(dithioisobiurets),	organic functional group wherein the number of
Bis(dithiobiureas), Poly(dithiobiurets),	carbon atoms ranges from 0 to 40, optionally
Poly(dithioisobiurets), and	having halogen or polarizing or water-
Poly(dithiobiureas) (S—S Bidentates, S—S	insolubilizing/solubilizing groups attached.
Tridentates, S—S Tetradentates)	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #19:	RR′—N—C(═S)—NR″—C(═S)—R″′ where R, R′, R″,
Thioacylthioureas, Thioaroylthioureas,	and R″′ represent H, NH₂, or any organic
Bis(thioacylthioureas),	functional group wherein the number of carbon
Bis(thioaroylthioureas),	atoms ranges from 0 to 40, optionally having
Poly(thioacylthioureas), and	halogen or polarizing or water-
Poly(thioaroylthioureas) (S—S Bidentates, S—	insolubilizing/solubilizing groups attached.
S Tridentates, S—S Tetradentates)	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #20:	R—C(═S)—S—S—C—(═S)—R′ where R, and R′
Dithioacyl disulfides, Bis(dithioacyl	represent H or any organic functional group
disulfides), and Poly(dithioacyl disulfides)	wherein the number of carbon atoms ranges
(S—S Bidentates, S—S Tridentates, S—S	from 0 to 40, optionally having halogen or
Tetradentates)	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
S Valence Stabilizer #21:	RR′—N—C(═S)—S—S—C(═S)—N—R″R″′ where R, R′,
Tetrathioperoxydicarbonic Diamides,	R″, R″′ represent H or any organic functional
Bis(tetrathioperoxydicarbonic diamides),	group wherein the number of carbon atoms
and poly(tetrathioperoxydicarbonic	ranges from 0 to 40, optionally having halogen
diamides) (S—S Bidentates, S—S Tridentates,	or polarizing or water-
S—S Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #22:	R—S—C(═S)—S—S—C(═S)—S—R′ for
Hexathio-, Pentathio-, and	hexathioperoxydicarbonic acids, R—O—C(═S)—S—
Tetrathioperoxydicarbonic Acids,	S—C(═S)—S—R′ for pentathioperoxydicarbonic
Bis(hexathio-, pentathio-, and	acids, and R—O—C(═S)—S—S—C(═S)—O—R′ for
tetrathioperoxydicarbonic acids),	tetrathioperoxydicarbonic acids, where R and R′
poly(hexathio-, pentathio-, and	represent H, NH₂or any organic functional
tetrathioperoxydicarbonic acids), and	group wherein the number of carbon atoms
derivatives thereof (S—S Bidentates, S—S	ranges from 0 to 40, optionally having halogen
Tridentates, S—S Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #23:	(RR′—N—)(RR″R″′—N—)P(═S)—S—S—P(═S)(—N—
Dithioperoxydiphosphoramide,	R″″R″″′)(—N—R″″″R″″″′), where R, R′, R″, R″′,
Bis(dithioperoxyphosphoramide), and	R″″, R″″′, R″″″, and R″″″′ represent H, NH₂or
Poly(dithioperoxydiphosphoramide) (S—S	any organic functional group wherein the
Bidentates, S—S Tridentates, S—S	number of carbon atoms ranges from 0 to 40,
Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S Valence Stabilizer #24:	(R—O—)(R′—O—)P(═S)—S—S—P(═S)(—O—R″)(—O—
Dithioperoxydiphosphoric Acids,	R″′); (R—O—)(R′—S—)P(═S)—S—S—P(═S)(—S—R″)(—O—
Bis(dithioperoxyphosphoric Acids),	R″′); or (R—S—)(R′—S—)P(═S)—S—S—P(═S)(—S—R″)(—
Poly(dithioperoxydiphosphoric Acids), and	S—R″′), where R, R′, R″, R″′, R″″, R″″′, R″″″,
derivatives thereof (S—S Bidentates, S—S	and R″″″′ represent H, NH₂or any organic
Tridentates, S—S Tetradentates)	functional group wherein the number of carbon
	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #25:	(R—O—)(R′—)P(═S)—NH—P(═S)(—R″)(—O—R″′); (R—
Dithioimidodiphosphonic Acids,	S—)(R′—)P(═S)—NH—P(═S)(—R″)(—O—R″′); or (R—
Dithiohydrazidodiphosphonic Acids,	S—)(R′—)P(═S)—NH—P(═S)(—R″)(—S—R″′) for
Bis(dithioimidodiphosphonic acids),	dithioimidodiphosphonic acids, and —NH—NH—
Bis(dithiohydrazidodiphosphonic acids),	derivatives for dithiohydrazidodiphosphonic
Poly(dithioimidodiphosphonic acids),	acids, where R, R′, R″, and R″′ represent H,
Poly(dithiohydrazidodiphosphonic acids),	NH₂or any organic functional group wherein
and derivatives thereof (S—S Bidentates, S—S	the number of carbon atoms ranges from 0 to
Tridentates, and S—S Tetradentates)	40, optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S Valence Stabilizer #26:	(RR′—N—)(R″—)P(═S)—NH—P(═S)(—R″′)(—N—
Dithioimidodiphosphonamides,	R″″R″″′) for dithioimidophosphonamides, and
Dithiohydrazidodiphosphonamides,	(RR′—N—)(R″—)P(═S)—NH—NH—P(═S)(—R″′)(—N—
Bis(dithioimidodiphosphonamides),	R″″R″″′) for
Bis(dithiohydrazidodiphosphonamides),	dithiohydrazidodiphosphonamides, where R, R′,
Poly(dithioimidodiphosphonamides), and	R″, R″′, R″″, and R″″′ represent H, NH₂or any
Poly(dithiohydrazidodiphosphonamides)	organic functional group wherein the number of
(S—S Bidentates, S—S Tridentates, S—S	carbon atoms ranges from 0 to 40, optionally
Tetradentates)	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #27:	(RR′—N—)(R″—)P(═S)—S—P(═S)(—R″′)(—N—
Dithiodiphosphonamides,	R″″R″″′), or (RR′—N—)(R″—)p(═S)—O—P—(═S)(—
Bis(dithiophosphonamides), and	R″′)(—N—R″″R″″′), where R, R′, R″, R″′, R″″,
Poly(dithiodiphosphonamides) (S—S	and R″″′ represent H, NH₂or any organic
Bidentates, S—S Tridentates, S—S	functional group wherein the number of carbon
Tetradentates)	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #28:	(R—O—)(R′—)P(═S)—O—P(═S)(—R″)(—O—R″′); (R—O—)
Dithiodiphosphonic Acids,	(R′—)P(═S)—S—P(═S)(—R″)(—O—R″′); (R—S—)(R′—)
Bis(dithioiphosphonic Acids),	P(═S)—O—P(═S)(—R″)(—S—R″′); or (R—S—)(R′—)
Poly(dithiodiphosphonic Acids), and	P(═S)—S—P(═S)(—R″)(—S—R″′); where R, R′, R″,
derivatives thereof (S—S Bidentates, S—S	and R″′ represent H, NH₂or any organic
Tridentates, S—S Tetradentates)	functional group wherein the number of carbon
	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #29:	(RR′—N—)(R″—)P(═S)—S—S—P(═S)(—R″′)(—N—
Dithioperoxydiphosphonamide,	R″″R″″′), where R, R′, R″, R″′, R″″, and R″″′
Bis(dithioperoxyphosphonamide), and	represent H, NH₂or any organic functional
Poly(dithioperoxydiphosphonamide) (S—S	group wherein the number of carbon atoms
Bidentates, S—S Tridentates, S—S	ranges from 0 to 40, optionally having halogen
Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #30:	(R—O—)(R′—)P(═S)—S—S—P(═S)(—R″)(—O—R″′); or
Dithioperoxydiphosphonic Acids,	(R—S—)(R′—)P(═S)—S—S—P(═S)(—R″)(—S—R″′),
Bis(dithioperoxyphosphonic Acids),	where R, R′, R″, and R″′ represent H, NH₂or
Poly(dithioperoxydiphosphonic Acids), and	any organic functional group wherein the
derivatives thereof (S—S Bidentates, S—S	number of carbon atoms ranges from 0 to 40,
Tridentates, S—S Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S Valence Stabilizer #31: Dithiophosphonic	(O═)PR(—S—R′)(—S—R″) or (S═)PR(—S—R′)(—O—
Acids (Phosphonodithioic Acids),	R″), where R, R′, and R″ represent H, NH₂or
Bis(dithiophosphonic Acids),	any organic functional group wherein the
Poly(dithiophosphonic Acids), and	number of carbon atoms ranges from 0 to 40,
derivatives thereof (S—S Bidentates, S—S	optionally having halogen or polarizing or
Tridentates, S—S Tetradentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S Valence Stabilizer #32:	(S═)PR(—S—R′)(—S—R″), where R, R′, and R″
Trithiophosphonic Acids	represent H, NH₂or any organic functional
(Phosphonotrithioic Acids),	group wherein the number of carbon atoms
Bis(trithiophosphonic Acids),	ranges from 0 to 40, optionally having halogen
Poly(trithiophosphonic Acids), and	or polarizing or water-
derivatives thereof (S—S Bidentates, S—S	insolubilizing/solubilizing groups attached.
Tridentates, S—S Tetradentates)	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #33:	(O═)PR(—S—S—R′)(—S—R″) or (S═)PR(—S—S—R′)(—
Phosphono(dithioperoxo)thioic Acids),	O—R″), where R, R′, and R″ represent H, NH₂or
Bis[phosphono(dithioperoxo)thioic Acids],	any organic functional group wherein the
Poly[phosphono(dithioperoxo)thioic	number of carbon atoms ranges from 0 to 40,
Acids], and derivatives thereof (S—S	optionally having halogen or polarizing or
Bidentates, S—S Tridentates, S—S	water-insolubilizing/solubilizing groups
Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S Valence Stabilizer #34:	(S═)PR(—S—S—R′)(—S—R″), where R, R′, and R″
Phosphono(dithioperoxo)dithioic Acids),	represent H, NH₂or any organic functional
Bis[phosphono(dithioperoxo)dithioic	group wherein the number of carbon atoms
Acids],	ranges from 0 to 40, optionally having halogen
Poly[phosphono(dithioperoxo)dithioic	or polarizing or water-
Acids], and derivatives thereof (S—S	insolubilizing/solubilizing groups attached.
Bidentates, S—S Tridentates, S—S	Ligand can also contain nonbinding N, O, S, or
Tetradentates)	P atoms.
S Valence Stabilizer #35:	R—S—R′CSOH or R—S—R′CSSH for S—
S—(Alkylthio)thiocarboxylic Acids, S—	(alkylthio)thiocarboxylic and S—
(Arylthio)thiocarboxylic Acids, and S,S—	(arylthio)thiocarboxylic acids, and HSOCR—S—
thiobisthiocarboxylic Acids (S—S Bidentates	R′COSH or HSSCR—S—R′CSSH for S,S—
and S—S Tridentates)	thiobisthiocarboxylic acids, where R and R′
	represent H or any organic functional group
	wherein the number of carbon atoms ranges
	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
S Valence Stabilizer #36:	R—S—S—R′CSOH or R—S—S—R′CSSH for S—
S—(Alkyldisulfido)thiocarboxylic Acids, S—	(alkyldisulfido)thiocarboxylic and S—
(Aryldisulfido)thiocarboxylic Acids, and	(aryldisulfido)thiocarboxylic acids, and
S,S′—Disulfidobisthiocarboxylic Acids (S—S	HSOCR—S—S—R′COSH or HSSCR—S—S—R′CSSH
Bidentates and S—S Tridentates)	for S,S′—disulfidobisthiocarboxylic acids, where
	R and R′ represent H or any organic functional
	group wherein the number of carbon atoms
	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #37:	R—CH(—SR″)—CH(—SR″′)—R′, and R—C(—
1,2-Dithiolates, Bis(1,2-dithiolates), and	SR″)═C(—SR″′)—R′, where R, R′, R″, and R″′
Poly(1,2-dithiolates) (S—S Bidentates, S—S	represent H, NH₂or any organic functional
Tridentates, S—S Tetradentates)	group wherein the number of carbon atoms
	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #38:	RN—C(═O)—CHR′—S—C(═S) for rhodanines, and
Rhodanines and Bis(rhodanines) (S—S	R—[N—C(═O)—CHR′—S—C(═S)]₂for
Bidentates and S—S Tetradentates)	bis(rhodanines), where R and R′ represent H,
	NH₂or any organic functional group wherein
	the number of carbon atoms ranges from 0 to
	40, optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S Valence Stabilizer #39:	RN═C(SH)(SH), where R represents H, NH₂or
Dithiocarbimates, Bis(dithiocarbimates),	any organic functional group wherein the
and Poly(dithiocarbimates) (S—S Bidentates,	number of carbon atoms ranges from 0 to 40,
S—S Tridentates, and S—S Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S Valence Stabilizer #40:	RS⁺═C(SH)(SH) or RS—C(═S)(SH), where R
Thioxanthates, Bis(thioxanthates), and	represents H, NH₂or any organic functional
Poly(thioxanthates) (S—S Bidentates and S—S	group wherein the number of carbon atoms
Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #41:	RO⁺═C(SH)(SH) or RO—C(═S)(SH), where R
Xanthates, Bis(xanthates), and	represents H, NH₂or any organic functional
Poly(xanthates) (S—S Bidentates and S—S	group wherein the number of carbon atoms
Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #42:	Typically RR′R″P═C(SH)(SH) [pentavalent P],
Phosphinodithioformates (S—S Bidentates)	although RR′P—C(═S)(SH) [trivalent P] may be
	acceptable in some situations, where R, R′, and
	R″ represent H, NH₂or any organic functional
	group wherein the number of carbon atoms
	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #43:	R—S—C(—S—R″)—O—R′ for dithioborates, R—S—C(—S—
Alkyl- and Aryl- Dithioborates,	R″)—S—R′ for trithioborates, and R—S—S—C(—S—
Trithioborates, Perthioborates,	R″)—S—R′ for perthioborates, where R, R′, and
Bis(dithioborates), Bis(trithioborates), and	R″ represent H, NH₂or any organic functional
Bis(perthioborates) (S—S Bidentates and S—S	group wherein the number of carbon atoms
Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #44:	R—C(—S—R″)—S—R′, where R, R′, and R″
Alkyl- and Aryl- Dithioboronates, and	represent H, NH₂or any organic functional
Bis(dithioboronates) (S—S Bidentates and S—S	group wherein the number of carbon atoms
Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #45:	(O═)As(—S—R)(—S—R′)(—S—R″) or (S═)As(—S—R)(—
Trithioarsonic Acids (Arsonotrithioic	S—R′)(—O—R″) for trithioarsonic acid; (O═)As(—
Acids), Dithioarsonic Acids	O—R)(—S—R′)(—S—R″) or (S═)As(—S—R)(—O—R′)(—
(Arsonodithioic Acids), Tetrathioarsonic	O—R″) for dithioarsonic acid, or (S═)As(—S—R)(—
Acids (Arsonotetrathioic Acids), and	S—R′)(—S—R″) for tetrathioarsonic acid, where R,
derivatives thereof (S—S Bidentates, S—S	R′, and R″ represent H, NH₂or any organic
Tridentates, S—S Tetradentates)	functional group wherein the number of carbon
	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #46:	(O═)Sb(—S—R)(—S—R′)(—S—R″) or (S═)Sb(—S—R)(—
Trithioantimonic Acids (Stibonotrithioic	S—R′)(—O—R″) for trithioantimonic acid;
Acids), Dithioantimonic Acids	(O═)Sb(—O—R)(—S—R′)(—S—R″) or (S═)Sb(—S—R)(—
(Stibonodithioic Acids), Tetrathioantimonic	O—R′)(—O—R″) for dithioantimonic acid, or
Acids (Stibonotetrathioic Acids), and	(S═)Sb(—S—R)(—S—R′)(—S—R″) for
derivatives thereof (S—S Bidentates, S—S	tetrathioantimonic acid, where R, R′, and R″
Tridentates, S—S Tetradentates)	represent H, NH₂or any organic functional
	group wherein the number of carbon atoms
	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S Valence Stabilizer #47:	RR′R″P═S for phosphine P—sulfides, and
Phosphine P—sulfides and Amino-	(RR′N)(R″R″′N)(R″″R″″′N)P═S for amino—
substituted Phosphine sulfides (S	substituted phosphine sulfides, where R, R′, R″,
Monodentates)	R″′, R″″, and R″″′ represent H, Cl, Br, NH₂or
	any organic functional group wherein the
	number of carbon atoms ranges from 0 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. (Rs are typically aromatic or
	heterocyclic for phosphine P-sulfides.) Ligand
	can also contain nonbinding N, O, S, or P
	atoms.
S Valence Stabilizer #48:	RR′R″As═S for arsine As-sulfides, and
Arsine As-sulfides and Amino-substituted	(RR′N)(R″R″′N)(R″″R″″′N)As═S for amino-
Arsine sulfides (S Monodentates)	substituted arsine sulfides, where R, R′, R″,
	R″′, R″″, and R″″′ represent H, Cl, Br, NH₂or
	any organic functional group wherein the
	number of carbon atoms ranges from 0 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. (Rs are typically aromatic or
	heterocyclic for arsine As-sulfides.) Ligand can
	also contain nonbinding N, O, S, or P atoms.
S Valence Stabilizer #49:	Thiols (HS—R, HS—R—SH, etc.), where R and R′
Thiolates (S Monodentates)	represent H or any organic functional group
	wherein the number of carbon atoms ranges
	from 0 to 35, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached.
S Valence Stabilizer #50:	Sulfide (—S²⁻) ligands bound directly to the high
Sulfide ligands (S Monodentates)	valence metal ion.
P Valence Stabilizer #1:	PH₃, PH₂R, PHR₂, and PR₃where R represents
Monophosphines (P Monodentates)	H or any organic functional group wherein the
wherein at least one Phosphorus Atom is a	number of carbon atoms ranges from 0 to 35,
Binding Site	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, As, O, S, or Se atoms.
P Valence Stabilizer #2:	R′—P—R—P—R″, where R, R′, and R″ represent H
Diphosphines (a P—P Bidentate) wherein at	or any organic functional group wherein the
least one Phosphorus Atom is a Binding	number of carbon atoms ranges from 0 to 35,
Site	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, As, O, S, or Se atoms.
P Valence Stabilizer #3:	R—P—R′—P—R″—P—R″′, where R, R′, R″, and R″′
Triphosphines (either P—P Bidentates or P-	represent H or any organic functional group
P—P Tridentates) wherein at least one	wherein the number of carbon atoms ranges
Phosphorus Atom is a Binding Site	from 0 to 35, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, P, As, O, S, or Se atoms.
P Valence Stabilizer #4:	R—P—R′—P—R″—P—R″′—P—R″″, where R, R′, R″,
Tetraphosphines (P—P Bidentates, P—P	R″′, and R″″ represent H or any organic
Tridentates, or P—P Tetradentates) wherein	functional group wherein the number of carbon
at least one Phosphorus Atom is a Binding	atoms ranges from 0 to 35, optionally having
Site	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, As, O,
	S, or Se atoms.
P Valence Stabilizer #5:	R—P—R′—P—R″—P—R″′—P—R″″—P—R″″′, where R, R′,
Pentaphosphines (P—P Bidentates, P—P	R″, R″′, R″″, and R″″′ represent H or any
Tridentates, or P—P Tetradentates) wherein	organic functional group wherein the number of
at least one Phosphorus Atom is a Binding	carbon atoms ranges from 0 to 35, optionally
Site	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, As, O,
	S, or Se atoms.
P Valence Stabilizer #6:	R—P—R′—P—R″—P—R″′—P—R″″—P—R″″′—P—R″″″,
Hexaphosphines (P—P Bidentates, P—P	where R, R′, R″, R″′, R″″, R″″′, and R″″″
Tridentates, P—P Tetradentates, or P—P	represent H or any organic functional group
Hexadentates) wherein at least one	wherein the number of carbon atoms ranges
Phosphorus Atom is a Binding Site	from 0 to 35, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, P, As, O, S, or Se atoms.
P Valence Stabilizer #7:	Five membered heterocyclic ring containing
Five-Membered Heterocyclic Rings	one, two, or three phosphorus atoms, all of
containing One, Two, or Three Phosphorus	which may or may not function as binding sites.
Atoms wherein at least one Phosphorus	Can include other ring systems bound to this
Atom is a Binding Site (P Monodentates or	heterocyclic ring, but they do not coordinate
P—P Bidentates)	with the stabilized, high valence metal ion.
	Ring can also contain O, S, N, As, or Se atoms.
	This 5-membered ring and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P Valence Stabilizer #8:	Six membered heterocyclic ring containing one,
Six-Membered Heterocyclic Rings	two, or three phosphorus atoms, all of which
containing One, Two, or Three Phosphorus	may or may not function as binding sites. Can
Atoms wherein at least one Phosphorus	include other ring systems bound to this
Atom is a Binding Site (P Monodentates or	heterocyclic ring, but they do not coordinate
P—P Bidentates)	with the stabilized, high valence metal ion.
	Ring can also contain O, S, N, As, or Se atoms.
	This 6-membered ring and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P Valence Stabilizer #9:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one, two, or three phosphorus atoms. In
containing One, Two, or Three Phosphorus	addition, ligand contains additional phosphorus-
Atoms at least one additional Phosphorus	containing substituents (usually phosphines)
Atom Binding Site not in a Ring (P	that constitute P binding sites. Can include
Monodentates, P—P Bidentates, P—P	other ring systems bound to the heterocyclic
Tridentates, P—P Tetradentates, or P—P	ring or to the P-containing substituent, but they
Hexadentates)	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	N, S, As or Se atoms. This 5-membered ring(s)
	and/or attached, uncoordinating rings and/or P-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P Valence Stabilizer #10:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one, two, or three phosphorus atoms. In
containing One, Two, or Three Phosphorus	addition, ligand contains additional phosphorus-
Atoms at least one additional Phosphorus	containing substituents (usually phosphines)
Atom Binding Site not in a Ring (P	that constitute P binding sites. Can include
Monodentates, P—P Bidentates, P—P	other ring systems bound to the heterocyclic
Tridentates, P—P Tetradentates, or P—P	ring or to the P-containing substituent, but they
Hexadentates)	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	N, S, As or Se atoms. This 6-membered ring(s)
	and/or attached, uncoordinating rings and/or P-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P Valence Stabilizer #11:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one, two, or three phosphorus atoms. In
containing One, Two, or Three Phosphorus	addition, ligand contains additional phosphorus-
Atoms at least one additional Phosphorus	containing rings that constitute P binding sites.
Atom Binding Site in a separate Ring (P	Can include other ring systems bound to the P-
Monodentates, P—P Bidentates, P—P	containing heterocyclic rings, but they do not
Tridentates, P—P Tetradentates, or P—P	coordinate with the stabilized, high valence
Hexadentates)	metal ion. Ring(s) can also contain O, N, S, As,
	or Se atoms. This 5-membered ring(s) and/or
	additional P-containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P Valence Stabilizer #12:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one, two, or three phosphorus atoms. In
containing One, Two, or Three Phosphorus	addition, ligand contains additional phosphorus-
Atoms at least one additional Phosphorus	containing rings that constitute P binding sites.
Atom Binding Site in a separate Ring (P	Can include other ring systems bound to the P-
Monodentates, P—P Bidentates, P—P	containing heterocyclic rings, but they do not
Tridentates, P—P Tetradentates, or P—P	coordinate with the stabilized, high valence
Hexadentates)	metal ion. Ring(s) can also contain O, N, S, As,
	or Se atoms. This 6-membered ring(s) and/or
	additional P-containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P Valence Stabilizer #13:	Macrocyclic ligands containing two, three, four,
two-, Three-, Four-, Five-, Six-, and Eight-	five, six, or eight phosphorus binding sites to
Membered Macrocyclics, Macrobicyclics,	valence stabilize the central metal ion. Can
and Macropolycyclics (including	include other hydrocarbon or ring systems
Catapinands, Cryptands, Cyclidenes, and	bound to this macrocyclic ligand, but they do
Sepulchrates) wherein all Binding Sites are	not coordinate with the stabilized, high valence
composed of Phosphorus and are not	metal ion. This ligand and/or attached,
contained in Component Heterocyclic	uncoordinating hydrocarbons/rings may or may
Rings (P—P Bidentates, P—P Tridentates, P—P	not have halogen or polarizing or water-
Tetradentates, and P—P Hexadentates)	insolubilizing/solubilizing groups attached.
P Valence Stabilizer #14:	Macrocyclic ligands containing a total of four,
Four-, six-, or Eight-Membered	six, or eight five-membered heterocyclic rings
Macrocyclics, Macrobicyclics, and	containing phosphorus binding sites. Can
Macropolycyclics (including Catapinands,	include other hydrocarbon/ring systems bound
Cryptands, Cyclidenes, and Sepulchrates)	to this macrocyclic ligand, but they do not
wherein all Binding Sites are composed of	coordinate with the stabilized, high valence
Phosphorus and are contained in	metal ion. This ligand and/or attached,
Component 5-Membered Heterocyclic	uncoordinating hydrocarbon/rings may or may
Rings (P—P Tridentates, P—P Tetradentates,	not have halogen or polarizing or water-
or P—P Hexadentates)	insolubilizing groups attached.
P Valence Stabilizer #15:	Macrocyclic ligands containing at least one 5-
Four-, six-, or Eight-Membered	membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and	heterocyclic rings provide phosphorus binding
Macropolycyclics (including Catapinands,	sites to valence stabilize the central metal ion.
Cryptands, Cyclidenes, and Sepulchrates)	Other phosphine binding sites can also be
wherein all Binding Sites are composed of	included in the macrocyclic ligand, so long as
Phosphorus and are contained in a	the total number of binding sites is four, six, or
Combination of 5-Membered Heterocyclic	eight. Can include other hydrocarbon/ring
Rings and Phosphine Groups (P—P	systems bound to this macrocyclic ligand, but
Tridentates, P—P Tetradentates, or P—P	they do not coordinate with the stabilized, high
Hexadentates)	valence metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
P Valence Stabilizer #16:	Macrocyclic ligands containing a total of four,
Four-, six-, or Eight-Membered	six, or eight six-membered heterocyclic rings
Macrocyclics, Macrobicyclics, and	containing phosphorus binding sites. Can
Macropolycyclics (including Catapinands,	include other hydrocarbon/ring systems bound
Cryptands, Cyclidenes, and Sepulchrates)	to this macrocyclic ligand, but they do not
wherein all Binding Sites are composed of	coordinate with the stabilized, high valence
Phosphorus and are contained in	metal ion. This ligand and/or attached,
Component 6-Membered Heterocyclic	uncoordinating hydrocarbon/rings may or may
Rings (P—P Tridentates, P—P Tetradentates,	not have halogen or polarizing or water-
or P—P Hexadentates)	insolubilizing groups attached.
P Valence Stabilizer #17:	Macrocyclic ligands containing at least one 6-
Four-, six-, or Eight-Membered	membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and	heterocyclic rings provide phosphorus binding
Macropolycyclics (including Catapinands,	sites to valence stabilize the central metal ion.
Cryptands, Cyclidenes, and Sepulchrates)	Other phosphine binding sites can also be
wherein all Binding Sites are composed of	included in the macrocyclic ligand, so long as
Phosphorus and are contained in a	the total number of binding sites is four, six, or
Combination of 6-Membered Heterocyclic	eight. Can include other hydrocarbon/ring
Rings and Phosphine Groups (P—P	systems bound to this macrocyclic ligand, but
Tridentates, P—P Tetradentates, or P—P	they do not coordinate with the stabilized, high
Hexadentates)	valence metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
O Valence Stabilizer #1:	R—O—C(═O)—S—S—C(═O)—O—R′, where R and R′
Dithioperoxydicarbonic Acids,	represent H, NH₂or any organic functional
Bis(dithioperoxydicarbonic acids),	group wherein the number of carbon atoms
poly(dithioperoxydicarbonic acids), and	ranges from 0 to 40, optionally having halogen
derivatives thereof (O—O Bidentates, O—O	or polarizing or water-
Tridentates, O—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #2:	(R—O—)(R′—)P(═O)—NH—P(═O)(—R″)(—O—R″′) for
Imidodiphosphonic Acids,	imidodiphosphonic acids, and (R—O—)(R′—)
Hydrazidodiphosphonic Acids,	P(═O)—NH—NH—P(═O)(—R″)(—O—R″′) for
Bis(imidodiphosphonic Acids),	hydrazidodiphosphonic acids; where R, R′, R″,
Bis(hydrazidodiphosphonic Acids),	and R″′ represent H, NH₂or any organic
Poly(imidodiphosphonic Acids),	functional group wherein the number of carbon
Poly(hydrazidodiphosphonic Acids), and	atoms ranges from 0 to 40, optionally having
derivatives thereof (O—O Bidentates, O—O	halogen or polarizing or water-
Tridentates, O—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #3:	(RR′—N—)(R″—)P(═O)—NH—P(═O)(—R″′)(—N—
Imidodiphosphonamides,	R″″R″″′) for imidodiphosphonamides, and —
Hydrazidodiphosphonamides,	NH—NH—derivatives for
Bis(imidodiphosphonamides),	hydrazidodiphosphonamides, where R, R′, R″,
Bis(hydrazidodiphosphonamides),	R″′, R″″, and R″″′ represent H, NH₂or any
Poly(imidodiphosphonamides), and	organic functional group wherein the number of
Poly(hydrazidodiphosphonamides) (O—O	carbon atoms ranges from 0 to 40, optionally
Bidentates, O—O Tridentates, O—O	having halogen or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #4:	(RR′—N—)(R″—)P(═O)—O—P(═O)(—R″′)(—N—
Diphosphonamides,	R″″R″″′), where R, R′, R″, R″′, R″″, and R″″′
Bis(diphosphonamides), and	represent H, NH₂or any organic functional
Poly(diphosphonamides) (O—O Bidentates,	group wherein the number of carbon atoms
O—O Tridentates, O—O Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #5:	R—O—C(═O)—O—R′, where R, and R′ represent H,
Carbonates and Bis(carbonates) (O—O	NH₂or any organic functional group wherein
Bidentates and O—O Tetradentates)	the number of carbon atoms ranges from 0 to
	40, optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
O Valence Stabilizer #6:	RR′N—NR″—C(═O)(OH), where R and R′
Carbazates (carbazides), Bis(carbazates),	represent H, NH₂or any organic functional
and Poly(carbazates) (O—O Bidentates, O—O	group wherein the number of carbon atoms
Tridentates, and O—O Tetradentates; or	ranges from 0 to 40, optionally having halogen
possibly N—O Bidentates, N—O Tridentates,	or polarizing or water-
and N—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #7:	(O═)As(—O—R)(—O—R′)(—O—R″), where R, R′, and
Arsonic Acids, Bis(arsonic acids),	R″ represent H, NH₂or any organic functional
Poly(arsonic acids), and derivatives thereof	group wherein the number of carbon atoms
(O—O Bidentates, O—O Tridentates, O—O	ranges from 0 to 40, optionally having halogen
Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #8:	R—O—C(—O—R″)—O—R′, where R, R′, and R″
Alkyl- and Aryl- Borates and Bis(borates)	represent H, NH₂or any organic functional
(O—O Bidentates and O—O Tetradentates)	group wherein the number of carbon atoms
	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #9:	R—C(—O—R″)—O—R′, where R, R′, and R″
Alkyl- and Aryl- Boronates and	represent H, NH₂or any organic functional
Bis(boronates) (O—O Bidentates and O—O	group wherein the number of carbon atoms
Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
O Valence Stabilizer #10:	RR′R″P═O for phosphine P-oxides, and
Phosphine P-oxides and Amino-substituted	(RR′N)(R″R″′N)(R″″R″″′N)P═O for amino-
Phosphine oxides (O Monodentates)	substituted phosphine oxides, where R, R′, R″,
	R″′,R″″, and R″″′, represent H, Cl, Br, NH₂or
	any organic functional group wherein the
	number of carbon atoms ranges from 0 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. (Rs are typically aromatic or
	heterocyclic for phosphine P-oxides.) Ligand
	can also contain nonbinding N, O, S, or P
	atoms.
O Valence Stabilizer #11:	RR′R″As═O for arsine As-oxides, and
Arsine As-oxides and Amino-substituted	(RR′N)(R″R″′N)(R″″R″″′N)As═O for amino-
Arsine oxides (O Monodentates)	substituted arsine oxides, where R, R′, R″, R″′,
	R″″, and R″″′ represent H, Cl, Br, NH₂or any
	organic functional group wherein the number of
	carbon atoms ranges from 0 to 40, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached. (Rs
	are typically aromatic or heterocyclic for arsine
	As-oxides.) Ligand can also contain nonbinding
	N, O, S, or P atoms.
O Valence Stabilizer #12:	Five membered heterocyclic ring containing one
Five-Membered Heterocyclic Rings	or two oxygen atoms, both of which may or
containing One or Two Oxygen Atoms	may not function as binding sites. Can include
wherein at least one Oxygen Atom is a	other ring systems bound to this heterocyclic
Binding Site (O Monodentates or O—O	ring, but they do not coordinate with the
Bidentates)	stabilized, high valence metal ion. Ring can
	also contain O, S, or P atoms. This 5-membered
	ring and/or attached, uncoordinating rings may
	or may not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
O Valence Stabilizer #13:	Six membered heterocyclic ring containing one
Six-Membered Heterocyclic Rings	or two oxygen atoms, both of which may or
containing One or Two Oxygen Atoms	may not function as binding sites. Can include
wherein at least one Oxygen Atom is a	other ring systems bound to this heterocyclic
Binding Site (O Monodentates or O—O	ring, but they do not coordinate with the
Bidentates)	stabilized, high valence metal ion. Ring can
	also contain O, S, or P atoms. This 6-membered
	ring and/or attached, uncoordinating rings may
	or may not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
O Valence Stabilizer #14:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one or two oxygen atoms. In addition, ligand
containing One or Two Oxygen Atoms and	contains additional oxygen-containing
having at least one additional Oxygen Atom	substituents (usually hydroxyl or ester groups)
Binding Site not in a Ring (O	that constitute O binding sites. Can include
Monodentates, O—O Bidentates, O	other ring systems bound to the heterocyclic
Tridentates, O Tetradentates, or O	ring or to the O-containing substituent, but they
Hexadentates)	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	S, or P atoms. This 5-membered ring(s) and/or
	attached, uncoordinating rings and/or O-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
O Valence Stabilizer #15:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one or two oxygen atoms. In addition, ligand
containing One or Two Oxygen Atoms and	contains additional oxygen-containing
having at least one additional Oxygen Atom	substituents (usually hydroxyl or ester groups)
Binding Site not in a Ring (O	that constitute O binding sites. Can include
Monodentates, O—O Bidentates, O	other ring systems bound to the heterocyclic
Tridentates, O Tetradentates, or O	ring or to the O-containing substituent, but they
Hexadentates)	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	S, or P atoms. This 6-membered ring(s) and/or
	attached, uncoordinating rings and/or O-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
O Valence Stabilizer #16:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one or two oxygen atoms. In addition, ligand
containing One or Two Oxygen Atoms and	contains additional oxygen-containing rings that
having at least one additional Oxygen Atom	constitute O binding sites. Can include other
Binding Site in a Separate Ring (O	ring systems bound to the O-containing
Monodentates, O—O Bidentates, O	heterocyclic rings, but they do not coordinate
Tridentates, O Tetradentates, or O	with the stabilized, high valence metal ion.
Hexadentates)	Ring(s) can also contain O, S, or P atoms. This
	5-membered ring(s) and/or additional O-
	containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
O Valence Stabilizer #17:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one or two oxygen atoms. In addition, ligand
containing One or Two Oxygen Atoms and	contains additional oxygen-containing rings that
having at least one additional Oxygen Atom	constitute O binding sites. Can include other
Binding Site in a Separate Ring (O	ring systems bound to the O-containing
Monodentates, O—O Bidentates, O	heterocyclic rings, but they do not coordinate
Tridentates, O Tetradentates, or O	with the stabilized, high valence metal ion.
Hexadentates)	Ring(s) can also contain O, S, or P atoms. This
	6-membered ring(s) and/or additional O-
	containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
O Valence Stabilizer #18:	Macrocyclic ligands containing four, five, six,
Four-, Five-, Six-, Seven-, Eight-, and Ten-	seven, eight, or ten oxygen binding sites to
Membered Macrocyclics, Macrobicyclics,	valence stabilize the central metal ion. Can
and Macropolycyclics (including	include other hydrocarbon or ring systems
Catapinands, Cryptands, Cyclidenes, and	bound to this macrocyclic ligand, but they do
Sepulchrates) wherein all Binding Sites are	not coordinate with the stabilized, high valence
composed of Oxygen (usually ester or	metal ion. This ligand and/or attached,
hydroxyl groups) and are not contained in	uncoordinating hydrocarbons/rings may or may
Component Heterocyclic Rings (O—O	not have halogen or polarizing or water-
Bidentates, O—O Tridentates, O—O	insolubilizing/solubilizing groups attached.
Tetradentates, and O—O Hexadentates)
O Valence Stabilizer #19:	Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, and Ten-	five, six, seven, eight, or ten five-membered
Membered Macrocyclics, Macrobicyclics,	heterocyclic rings containing oxygen binding
and Macropolycyclics (including	sites. Can include other hydrocarbon or ring
Catapinands, Cryptands, Cyclidenes, and	systems bound to this macrocyclic ligand, but
Sepulchrates) wherein all Binding Sites are	they do not coordinate with the stabilized, high
composed of Oxygen and are contained in	valence metal ion. This ligand and/or attached,
Component 5-Membered Heterocyclic	uncoordinating hydrocarbons/rings may or may
Rings (O—O Bidentates, O—O Tridentates,	not have halogen or polarizing or water-
O—O Tetradentates, and O—O Hexadentates)	insolubilizing/solubilizing groups attached.
O Valence Stabilizer #20:	Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, and Ten-	five, six, seven, eight, or ten six-membered
Membered Macrocyclics, Macrobicyclics,	heterocyclic rings containing oxygen binding
and Macropolycyclics (including	sites. Can include other hydrocarbon or ring
Catapinands, Cryptands, Cyclidenes, and	systems bound to this macrocyclic ligand, but
Sepulchrates) wherein all Binding Sites are	they do not coordinate with the stabilized, high
composed of Oxygen and are contained in	valence metal ion. This ligand and/or attached,
Component 6-Membered Heterocyclic	uncoordinating hydrocarbons/rings may or may
Rings (O—O Bidentates, O—O Tridentates,	not have halogen or polarizing or water-
O—O Tetradentates, and O—O Hexadentates)	insolubilizing/solubilizing groups attached.
N—S Valence Stabilizer #1:	RC(═NH)SR′, where R and R′ represent H or
Thioimidates, Dithioimidates,	any organic functional group wherein the
Polythioimidates, and Derivatives of	number of carbon atoms ranges from 0 to 40,
Thioimidic Acid (N—S Bidentates and N—S	optionally having halogen or polarizing or
Tetradentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—S Valence Stabilizer #2:	RR′—N—C(═NH)—NR″—CS—NR″′R″″ for
Thioguanylureas, Guanidinothioureas,	thioguanylureas, and RR′—N—C(═NH)—NR″—NH—
Bis(thioguanylureas),	CS—NR″′R″″ for guanidinothioureas, where R,
Bis(guanidinothioureas),	R′, R″, R″′, and R″″ represent H, NH₂, or any
Poly(thioguanylureas), and	organic functional group wherein the number of
Poly(guanidinothioureas) (N—S Bidentates	carbon atoms ranges from 0 to 40, optionally
and N—S Tetradentates)	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #3:	RR′—N—C(═NH)—NR″—CS—R″′ for N—
Amidinothioamides, Guanidinothioamides,	amidinothioamides, or RR′—N—C(═NH)—
Bis(amidinothioamides),	CR″R″′—CS—N—R″″R″″′ for 2—
Bis(guanidinothioamides),	amidinothioacetamides, and RR′—N—C(═NH)—
Poly(amidinothioamides), and	NR″—NH—CS—R″′ for guanidinothioamides,
Poly(guanidinothioamides) (including both	where R, R′, R″, R″′, R″″, and R″″′ represent
N-amidinothioamides and 2-	H, NH₂, or any organic functional group
amidinothioacetamides) (N—S Bidentates	wherein the number of carbon atoms ranges
and N—S Tetradentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—S Valence Stabilizer #4:	R—C(═NH)—NR′—CS—R″, where R, R′, and R″,
Imidoylthioamides,	represent H or any organic functional group
Bis(imidoylthioamides), and	wherein the number of carbon atoms ranges
Poly(imidoylthioamides) (N—S Bidentates	from 0 to 40, optionally having halogen or
and N—S Tetradentates)	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—S Valence Stabilizer #5:	RR′NCSNR″R″′, where R, R′, R″, and R″′
Thioureas, Bis(thioureas), and	represent H, NH₂, or any organic functional
Poly(thioureas), including Thiourylene	group wherein the number of carbon atoms
Complexes (N—S Bidentates, N—S	ranges from 0 to 40, optionally having halogen
Tridentates, and N—S Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #6:	RCSNR′R″, where R, R′, and R″ represent H,
Thiocarboxamides, Bis(thiocarboxamides),	NH₂, or any organic functional group wherein
and Poly(thiocarboxamides) (N—S	the number of carbon atoms ranges from 0 to
Bidentates, N—S Tridentates, and N—S	40, optionally having halogen or polarizing or
Tetradentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—S Valence Stabilizer #7:	RR′—N—S(═NH)—N—R″R″′, where R, R′, R″, and
Imidosulfurous Diamides and	R″′ represent H or any organic functional group
Bis(imidosulfurous diamides) (N—S	wherein the number of carbon atoms ranges
Bidentates, N—S Tridentates, and N—S	from 0 to 40, optionally having halogen or
Tetradentates)	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—S Valence Stabilizer #8:	R—N═S═N—R′, where R and R′ represent H or
Sulfurdiimines, Bis(sulfurdiimines), and	any organic functional group wherein the
Poly(sulfurdiimines) (N—S Bidentates, N—S	number of carbon atoms ranges from 0 to 40,
Tridentates, and N—S Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—S Valence Stabilizer #9:	(NH═)PR(OR′)(SR″) for phosphonimidothioic
Phosphonimidothioic Acid,	acid and (NH═)PR(SR′)(SR″) for
Phosphonimidodithioic Acid,	phosphonimidodithioic acid, where R, R′, and
Bis(Phosphonimidothioic acid);	R″ represent H or any organic functional group
Bis(Phosphonimidodithioic acid), and	wherein the number of carbon atoms ranges
derivatives thereof (N—S Bidentates, N—S	from 0 to 40, optionally having halogen or
Tetradentates)	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—S Valence Stabilizer #10:	(S═)PR(—NR′R″)(—NR″′R″″), where R, R′, R″,
Phosphonothioic Diamides,	R″′, and R″″ represent H or any organic
Bis(phosphonothioic diamides), and	functional group wherein the number of carbon
Poly(phosphonothioic diamides) (N—S	atoms ranges from 0 to 40, optionally having
Bidentates and N—S Tetradentates)	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #11:	(S═)PR(—NR′R″)(—OR″′) or (O═)PR(—NR′R″)(—
Phosphonamidothioic Acid,	SR″′) for phosphonamidothioic acid, (S═)PR(—
Phosphonamidimidodithioic Acid,	NR′R″)(—SR″′) for phosphonamidimidodithioic
Bis(phosphonamidothioic acid),	acid, where R, R′, R″, and R″′ represent H or
Bis(phosphonamidimidodithioic acid),	any organic functional group wherein the
poly(phosphonamidothioic acid), and	number of carbon atoms ranges from 0 to 40,
poly(phosphonamidimidodithioic acid), and	optionally having halogen or polarizing or
derivatives thereof (N—S Bidentates and N—S	water-insolubilizing/solubilizing groups
Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—S Valence Stabilizer #12:	R—C(═S)—CR′═CR″—NHR″′, where R, R′, R″,
Beta-Aminothiones (N-Substituted 3-	and R″′ represent H, or any organic functional
amino-2-propenethioaldehydes), Bis(beta-	group wherein the number of carbon atoms
aminothiones), and Poly(beta-	ranges from 0 to 40, optionally having halogen
aminothiones) (N—S Bidentates and N—S	or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #13:	RR′—N—C(═S)—CR″═C(—NHR″′)R″″ for 3-
3-Aminothioacrylamides (3-Amino-2-	aminothioacrylamides, and RR′—N—C(═S)—
thiopropenamides), 3,3-	CR″═C(—NHR″′)(—NR″″R″″′) for 3,3-
Diaminothioacrylamides, Bis(3-	diaminothioacrylamides, where R, R′, R″, R″′,
aminothioacrylamides), Bis(3,3-	R″″, R″″′ represent H, NH₂, or any organic
diaminoacrylamides), Poly(3-	functional group wherein the number of carbon
aminothioacrylamides), and Poly(3,3-	atoms ranges from 0 to 40, optionally having
diaminothioacrylamides) (N—S Bidentates	halogen or polarizing or water-
and N—S Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #14:	R—O—C(═S)—CR′═C(—NHR″)R″′ or R—S—C(═S)—
3-Aminothioacrylic Acids (3-Amino-2-	CR′═C(—NHR″)R″′ for 3-aminothioacrylic
thiopropenoic acids), 3-Mercapto-3-	acids, and R—O—C(═S)—CR′═C(—NHR″)(—S—R″′)
aminothioacrylic acids, Bis(3-	or R—S—C(═S)—CR′═C(—NHR″)(—S—R″′) for 3-
aminothioacrylic acids), Bis(3-Hydroxy-3-	mercapto-3-aminothioacrylic acids, where R,
aminothioacrylic acids), Poly(3-	R′, R″, and R″′ represent H, NH₂, or any
aminothioacrylic acids), and Poly(3-	organic functional group wherein the number of
Hydroxy-3-aminothioacrylic acids), and	carbon atoms ranges from 0 to 40, optionally
derivatives thereof (N—S Bidentates and N—S	having halogen or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #15:	R—C(═S)—N═CHR′, where R′ represents an
N-Thioacyl Benzylidenimines, Bis(N-	aromatic derivative (i.e. —C₆H₅), and R represent
thioacyl benzylidenimines), and Poly(N-	H, NH₂, or any organic functional group
thioacyl benzylidenimines) (N—S Bidentates	wherein the number of carbon atoms ranges
and N—S Tetradentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—S Valence Stabilizer #16:	R—C(═S)—C(═NOH)—R′, where R and R′
Thiocarbonyl oximes, Bis(thiocarbonyl	represent H, NH₂, or any organic functional
oximes), and Poly(thiocarbonyl oximes)	group wherein the number of carbon atoms
(N—S Bidentates, N—S Tridentates, and N—S	ranges from 0 to 40, optionally having halogen
Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #17:	R—CH(—SH)—C(═NOH)—R′, where R, R′, and R″
Mercapto oximes, Bis(mercapto oximes),	represent H, NH₂, or any organic functional
and Poly(mercapto oximes) (including 2-	group wherein the number of carbon atoms
sulfur heterocyclic oximes) (N—S	ranges from 0 to 40, optionally having halogen
Bidentates, N—S Tridentates, N—S	or polarizing or water-
Tetradentates, and N—S Hexadentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—S Valence Stabilizer #18:	o—(O₂N—)(HS—)Ar, where Ar represents an
2-Nitrothiophenols (2-nitrobenzenethiols)	aromatic group or heterocyclic wherein the
(N—S Bidentates)	number of carbon atoms ranges from 6 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—S Valence Stabilizer #19:	o—(NC—(CH₂)_0-1)(HS—)Ar, where Ar represents
2-Nitrilothiophenols (N—S Bidentates)	an aromatic group or heterocyclic wherein the
	number of carbon atoms ranges from 6 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—S Valence Stabilizer #20:	R—C(═S)—NHNR′R″, where R, R′, and R″
Thiohydrazides, Bis(thiohydrazides), and	represent H or any organic functional group
Poly(thiohydrazides) (N—S Bidentates and	wherein the number of carbon atoms ranges
N—S Tetradentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—S Valence Stabilizer #21:	RR′—N—C(═S)—NHNR″R″′, where R, R′, and R″
Thiosemicarbazides,	represent H or any organic functional group
Bis(thiosemicarbazides), and	wherein the number of carbon atoms ranges
Poly(thiosemicarbazides) (N—S Bidentates,	from 0 to 40, optionally having halogen or
N—S Tetradentates, and N—S Hexadentates)	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—S Valence Stabilizer #22:	Macrocyclic ligands containing five, seven, or
Five-, Seven-, or Nine-Membered	nine binding sites composed of nitrogen and
Macrocyclics, Macrobicyclics, and	sulfur to valence stabilize the central metal ion.
Macropolycyclics (including Catapinands,	Can include other hydrocarbon or ring systems
Cryptands, Cyclidenes, and Sepulchrates)	bound to this macrocyclic ligand, but they do
wherein all Binding Sites are composed of	not coordinate with the stabilized, high valence
Nitrogen (usually amine or imine groups) or	metal ion. This ligand and/or attached,
Sulfur (usually thiols, mercaptans, or	uncoordinating hydrocarbons/rings may or may
thiocarbonyls) and are not contained in	not have halogen or polarizing or water-
Component Heterocyclic Rings (N—S	insolubilizing/solubilizing groups attached.
Tridentates, N—S Tetradentates, and N—S
Hexadentates)
N—S Valence Stabilizer #23:	Macrocyclic ligands containing a total of five or
Five-, or Seven-Membered Macrocyclics,	seven heterocyclic rings containing nitrogen or
Macrobicyclics, and Macropolycyclics	sulfur binding sites. Can include other
(including Catapinands, Cryptands,	hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Nitrogen or	with the stabilized, high valence metal ion. This
Sulfur and are contained in Component	ligand and/or attached, uncoordinating
Heterocyclic Rings (N—S Tridentates, N—S	hydrocarbon/rings may or may not have halogen
Tetradentates, or N—S Hexadentates)	or polarizing or water-insolubilizing groups
	attached.
N—S Valence Stabilizer #24:	Macrocyclic ligands containing at least one
Five-, Seven-, or Nine-Membered	heterocyclic ring. These heterocyclic rings
Macrocyclics, Macrobicyclics, and	provide nitrogen or sulfur binding sites to
Macropolycyclics (including Catapinands,	valence stabilize the central metal ion. Other
Cryptands, Cyclidenes, and Sepulchrates)	amine, imine, thiol, mercapto, or thiocarbonyl
wherein all Binding Sites are composed of	binding sites can also be included in the
Nitrogen or Sulfur and are contained in a	macrocyclic ligand, so long as the total number
Combination of Heterocyclic Rings and	of binding sites is five, seven, or nine. Can
Amine, Imine, Thiol, Mercapto, or	include other hydrocarbon/ring systems bound
Thiocarbonyl Groups (N—S Tridentates, N—S	to this macrocyclic ligand, but they do not
Tetradentates, or N—S Hexadentates)	coordinate with the stabilized, high valence
	metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
N—O Valence Stabilizer #1:	RC(═NH)OR′, where R and R′ represent H or
Imidates, Diimidates, Polyimidates, and	any organic functional group wherein the
Derivatives of Imidic Acid (N—O Bidentates	number of carbon atoms ranges from 0 to 40,
and N—O Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—O Valence Stabilizer #2:	RR′NC(═NH)OR″, where R, R′, and R″
Pseudoureas, bis(pseudoureas), and	represent H, NH₂, or any organic functional
poly(pseudoureas) (N—O Bidentates and N—	group wherein the number of carbon atoms
O Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #3:	RR′NC(═NH)CR″R″′(CO)OR″″, where R, R′,
2-Amidinoacetates, Bis(2-amidinoacetates),	R″, R″′, and R″″ represent H, NH₂, or any
and Poly(2-amidinoacetates) (N—O	organic functional group wherein the number of
Bidentates and N—O Tetradentates)	carbon atoms ranges from 0 to 40, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #4:	RR′NCONR″R″′, where R, R′, R″, and R″′
Ureas, Bis(ureas), and Poly(ureas),	represent H, NH₂, or any organic functional
including Urylene Complexes (N—O	group wherein the number of carbon atoms
Bidentates, N—O Tridentates, and N—O	ranges from 0 to 40, optionally having halogen
Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #5:	(NH═)PR(OR′)(OR″), where R, R′, and R″
Phosphonimidic Acid, Bis(phosphonimidic	represent H, NH₂, or any organic functional
acid), Poly(phosphonimidic acid), and	group wherein the number of carbon atoms
derivatives thereof (N—O Bidentates and N—	ranges from 0 to 40, optionally having halogen
O Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms
N—O Valence Stabilizer #6:	(O═)PR(—NR′R″)(—OR″′) for phosphonamidic
Phosphonamidic Acid, Phosphonic	acid and (O═)PR(—NR′R″)(—NR″′R″″) for
Diamide, Bis(Phosphonamidic Acid),	phosphonic diamide, where R, R′, R″, R″′, and
Bis(Phosphonic Diamide),	R″″ represent H, NH₂, or any organic functional
Poly(phosphonamidic acid),	group wherein the number of carbon atoms
poly(phosphonic diamide), and derivatives	ranges from 0 to 40, optionally having halogen
thereof (N—O Bidentates and N—O	or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #7:	R—C(═O)—CR′═C(—NHR″)R″′, where R, R′, R″,
Beta-Ketoamines (N-Substituted 3-amino-	and R″′ represent H, or any organic functional
2-propenals), Bis(beta-ketoamines), and	group wherein the number of carbon atoms
Poly(beta-ketoamines) (N—O Bidentates and	ranges from 0 to 40, optionally having halogen
N—O Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #8:	RR′ —N—C(═O)—CR″═C(—NHR″′)R″″ for 3-
3-Aminoacrylamides (3-Amino-2-	aminoacrylamides, and RR′—N—C(═O)—CR″═C(—
propenamides), 3,3-Diaminoacrylamides,	NHR″′)(—NR″″R″″′) for 3,3-
Bis(3-aminoacrylamides), Bis(3,3-	diaminoacrylamides, where R, R′, R″, R″′, R″″,
diaminoacrylamides), Poly(3-	and R″″′ represent H, NH₂, or any organic
aminoacrylamides), and Poly(3,3-	functional group wherein the number of carbon
diaminoacrylamides) (N—O Bidentates and	atoms ranges from 0 to 40, optionally having
N—O Tetradentates)	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #9:	R—O—C(═O)—CR′═C(—NHR″)R″′ for 3-
3-Aminoacrylic Acids (3-Amino-2-	aminoacrylic acids, and R—O—C(═O)—CR′═C(—
propenoic acids), 3-Hydroxy-3-	NHR″)(—O—R″′) for 3-hydroxy-3-aminoacrylic
aminoacrylic acids, Bis(3-aminoacrylic	acids, where R, R′, R″, and R″′ represent H,
acids), Bis(3-Hydroxy-3-aminoacrylic	NH₂, or any organic functional group wherein
acids), Poly(3-aminoacrylic acids), and	the number of carbon atoms ranges from 0 to
Poly(3-Hydroxy-3-aminoacrylic acids), and	40, optionally having halogen or polarizing or
derivatives thereof (N—O Bidentates and N—	water-insolubilizing/solubilizing groups
O Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—O Valence Stabilizer #10:	R—C(═O)—N═CHR′, where R′ represents an
N-Acyl Benzylidenimines, Bis(N-acyl	aromatic derivative (i.e. —C₆H₅), and R represent
benzylidenimines), and Poly(N-acyl	H, NH₂, or any organic functional group
benzylidenimines) (N—O Bidentates and N—	wherein the number of carbon atoms ranges
O Tetradentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—O Valence Stabilizer #11:	o—(O₂N—)(RR′N—)Ar, where Ar represents an
2-Nitroanilines (N—O Bidentates)	aromatic group or heterocyclic wherein the
	number of carbon atoms ranges from 6 to 40,
	and R and R′ represent H, NH2, or alkyl or aryl
	hydrocarbon groups wherein the number of
	carbon atoms range from 0 to 25, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #12:	o—(NC—(CH₂)_0-1)(HO—)Ar, where Ar represents
2-Nitrilophenols (N—O Bidentates). Also	an aromatic group or heterocyclic wherein the
includes acylcyanamides.	number of carbon atoms ranges from 6 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
N—O Valence Stabilizer #13:	Het N⁺—O⁻for amine N—oxides, and R—N═N⁺(—O⁻)—
Amine N—Oxides and Diazine N—Oxides	R′ for diazine N—oxides (azoxy compounds),
(Azoxy componds) (N—O Bidentates, N—O	where Het represents a nitrogen-containing
Tridentates, and N—O Tetradentates)	heterocyclic derivative wherein the number of
	carbon atoms ranges from 4 to 40, and R and R′
	represent separate or the same aromatic
	functionalities, both Het and R,R′ optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
N—O Valence Stabilizer #14:	R—C(═O)—NHNR′R″, where R, R′, and R″
Hydrazides, Bis(hydrazides), and	represent H or any organic functional group
Poly(hydrazides) (N—O Bidentates and N—O	wherein the number of carbon atoms ranges
Tetradentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—O Valence Stabilizer #15:	RR′—N—C(═O)—NHNR″R″′, where R, R′, and R″
Semicarbazides, Bis(semicarbazides), and	represent H or any organic functional group
Poly(semicarbazides) (N—O Bidentates, N—O	wherein the number of carbon atoms ranges
Tetradentates, and N—O Hexadentates)	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
N—O Valence Stabilizer #16:	Macrocyclic ligands containing five, seven, or
Five-, Seven-, or Nine-Membered	nine binding sites composed of nitrogen and
Macrocyclics, Macrobicyclics, and	oxygen to valence stabilize the central metal
Macropolycyclics (including Catapinands,	ion. Can include other hydrocarbon or ring
Cryptands, Cyclidenes, and Sepulchrates)	systems bound to this macrocyclic ligand, but
wherein all Binding Sites are composed of	they do not coordinate with the stabilized, high
Nitrogen (usually amine or imine groups) or	valence metal ion. This ligand and/or attached,
Oxygen (usually hydroxy, carboxy, or	uncoordinating hydrocarbons/rings may or may
carbonyl groups) and are not contained in	not have halogen or polarizing or water-
Component Heterocyclic Rings (N—O	insolubilizing/solubilizing groups attached.
Tridentates, N—O Tetradentates, and N—O
Hexadentates)
N—O Valence Stabilizer #17:	Macrocyclic ligands containing a total of five or
Five-, or Seven-Membered Macrocyclics,	seven heterocyclic rings containing nitrogen or
Macrobicyclics, and Macropolycyclics	oxygen binding sites. Can include other
(including Catapinands, Cryptands,	hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Nitrogen or	with the stabilized, high valence metal ion. This
Oxygen and are contained in Component	ligand and/or attached, uncoordinating
Heterocyclic Rings (N—O Tridentates, N—O	hydrocarbon/rings may or may not have halogen
Tetradentates, or N—O Hexadentates)	or polarizing or water-insolubilizing groups
	attached.
N—O Valence Stabilizer #18:	Macrocyclic ligands containing at least one
Five-, Seven-, or Nine-Membered	heterocyclic ring. These heterocyclic rings
Macrocyclics, Macrobicyclics, and	provide nitrogen or oxygen binding sites to
Macropolycyclics (including Catapinands,	valence stabilize the central metal ion. Other
Cryptands, Cyclidenes, and Sepulchrates)	amine, imine, hydroxy, carboxy, or carbonyl
wherein all Binding Sites are composed of	binding sites can also be included in the
Nitrogen or Oxygen and are contained in a	macrocyclic ligand, so long as the total number
Combination of Heterocyclic Rings and	of binding sites is five, seven, or nine. Can
Amine, Imine, Hydroxy, Carboxy, or	include other hydrocarbon/ring systems bound
Carbonyl Groups (N—O Tridentates, N—O	to this macrocyclic ligand, but they do not
Tetradentates, or N—O Hexadentates)	coordinate with the stabilized, high valence
	metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
S—O Valence Stabilizer #1:	RR′—N—C(═S)—NR″—C(═O)—NR″′R″″ for
Thiobiurets (Thioimidodicarbonic	thiobiurets, and RR′—N—C(═S)—NR″—NH—C(═O)—
Diamides), Thioisobiurets, Thiobiureas,	NR″′R″″ for thiobiureas, where R, R′, R″, R″′,
Thiotriurets, Thiotriureas, Bis(thiobiurets),	and R″″ represent H, NH₂, or any organic
Bis(thioisobiurets), Bis(thiobiureas),	functional group wherein the number of carbon
Poly(thiobiurets), Poly(thioisobiurets),	atoms ranges from 0 to 40, optionally having
Poly(thiobiureas) (S—O Bidentates, S—O	halogen or polarizing or water-
Tridentates, S—O Tetradentates), and (3-	insolubilizing/solubilizing groups attached.
formamidino thiocarbamides)	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #2:	RR′—N—C(═S)—NR″—C(═O)—R″′ for acyl—and
Acylthioureas, Aroylthioureas,	aroylthioureas, and RR′—N—C(═O)—NR″—C(═S)—
Thioacylureas, Thioaroylureas,	R″′for thioacyl—and thioaroylureas, where R,
Bis(acylthioureas), Bis(aroylthioureas),	R′, R″, and R″′ represent H, NH₂, or any
Bis(thioacylureas), Bis(thioaroylureas),	organic functional group wherein the number of
Poly(thioacylthioureas),	carbon atoms ranges from 0 to 40, optionally
Poly(thioaroylthioureas),	having halogen or polarizing or water-
Poly(thioacylureas), and	insolubilizing/solubilizing groups attached.
Poly(thioaroylureas) (S—O Bidentates, S—O	Ligand can also contain nonbinding N, O, S, or
Tridentates, S—O Tetradentates)	P atoms.
S—O Valence Stabilizer #3:	RC(═S)—NR′—C(═O)—R″ for
Thioimidodialdehydes,	thioimidodialdehydes, and RC(═S)—NR′—NH—
Thiohydrazidodialdehydes (thioacyl	C(═O)—R″ for thiohydrazidodialdehydes
hydrazides), Bis(thioimidodialdehydes),	(thioacyl hydrazides), where R, R′, and R″
Bis(thiohydrazidodialdehydes),	represent H, NH₂, or any organic functional
Poly(thioimidodialdehydes), and	group wherein the number of carbon atoms
Poly(thiohydrazidodialdehydes) (S—O	ranges from 0 to 40, optionally having halogen
Bidentates, S—O Tridentates, S—O	or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #4:	R—O—C(═S)—NR′—C(═O)—O—R″or R—S—C(═S)—
Thioimidodicarbonic acids,	NR′—C(═O)—S—R″ for thioimidodicarbonic acids,
Thiohydrazidodicarbonic acids,	and R—O—C(═S)—NR′—NH—C(═O)—O—R″ or R—S—
Bis(thioimidodicarbonic acids),	C(═S)—NR′—NH—C(═O)—S—R″ for
Bis(thiohydrazidodicarbonic acids),	thiohydrazidodicarbonic acids, where R, R′, and
Poly(thioimidodicarbonic acids),	R″ represent H, NH₂, or any organic functional
Poly(thiohydrazidodicarbonic acids) and	group wherein the number of carbon atoms
derivatives thereof (S—O Bidentates, S—O	ranges from 0 to 40, optionally having halogen
Tridentates, S—O Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #5:	R—C(═S)—C(═O)—R′ where R and R′ represent H,
1,2-Monothioketones (Monothiolenes,	NH₂, or any organic functional group wherein
Monothio—alpha—ketonates), 1,2,3-	the number of carbon atoms ranges from 0 to
Monothioketones, 1,2,3-Dithioketones,	40, optionally having halogen or polarizing or
Monothiotropolonates, ortho-	water-insolubilizing/solubilizing groups
Monothioquinones, Bis(1,2-	attached. Ligand can also contain nonbinding N,
Monothioketones), and Poly(1,2-	O, S, or P atoms.
Monothioketones) (S—O Bidentates, S—O
Tridentates, S—O Tetradentates)
S—O Valence Stabilizer #6:	RR′—N—C(═S)—S—S—C(═O)—N—R″R″′ for
Trithioperoxydicarbonic Diamides,	trithioperoxydicarbonic diamides, and RR′—N—
Dithioperoxydicarbonic Diamides,	C(═O)—S—S—C(═O)—N—R″R″′ for
Bis(trithioperoxydicarbonic diamides),	dithioperoxydicarbonic diamides, where R, R′,
Bis(dithioperoxydicarbonic diamides),	R″, R″′ represent H or any organic functional
poly(trithioperoxydicarbonic diamides) and	group wherein the number of carbon atoms
poly(dithioperoxydicarbonic diamides) (S—O	ranges from 0 to 40, optionally having halogen
Bidentates, S—O Tridentates, S—O	or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #7:	R—O—C(═S)—S—C(═O)—O—R′, where R and R′
Diithiodicarbonic Acids,	represent H, NH₂or any organic functional
Bis(dithiodicarbonic acids),	group wherein the number of carbon atoms
Poly(dithiodicarbonic acids), and	ranges from 0 to 40, optionally having halogen
derivatives thereof (S—O Bidentates, S—O	or polarizing or water-
Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #8:	R—O—C(═S)—S—S—C(═O)—O—R′, where R and R′
Trithioperoxydicarbonic Acids,	represent H, NH₂or any organic functional
Bis(trithioperoxydicarbonic acids),	group wherein the number of carbon atoms
poly(trithioperoxydicarbonic acids), and	ranges from 0 to 40, optionally having halogen
derivatives thereof (S—O Bidentates, S—O	or polarizing or water-
Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #9:	(RR′—N—)(R″R″′—N—)P(═S)—S—S—P(═O)(—N—
Monothioperoxydiphosphoramide,	R″″R″″′)(—N—R″″″R″″″′), where R, R′, R″, R″′,
Bis(monothioperoxyphosphoramide), and	R″″, R″″′, R″″″, and R″″″′ represent H, NH₂or
Poly(monothioperoxydiphosphoramide) (S—O	any organic functional group wherein the
Bidentates, S—O Tridentates, S—O	number of carbon atoms ranges from 0 to 40,
Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S—O Valence Stabilizer #10:	(R—O—)(R′—O—)P(═S)—S—S—P(═O)(—O—R″)(—O—
Monothioperoxydiphosphoric Acids,	R″′); (R—O—)(R′—S—)P(═S)—S—S—P(═O)(—S—R″)(—
Bis(monothioperoxyphosphoric Acids),	O—R″′); or (R—S—)(R′—S—)P(═S)—S—S—P(═O)(—S—
Poly(monothioperoxydiphosphoric Acids),	R″)(—S—R″′), where R, R′, R″, R″′, R″″, R″″′,
and derivatives thereof (S—O Bidentates, S—O	R″″″, and R″″″′ represent H, NH₂or any
Tridentates, S—O Tetradentates)	organic functional group wherein the number of
	carbon atoms ranges from 0 to 40, optionally
	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #11:	(R—O—)(R′—)P(═S)—NH—P(═O)(—R″)(—O—R″′); (R—
Monothioimidodiphosphonic Acids,	S—)(R′—)P(═S)—NH—P(═O)(—R″)(—O—R″′); or (R—
Monothiohydrazidodiphosphonic Acids,	S—)(R′—)P(═S)—NH—P(═O)(—R″)(—S—R″′) for
Bis(monothioimidodiphosphonic Acids),	monothioimidodiphosphonic acids, and —NH—
Bis(monothiohydrazidodiphosphonic	NH—derivatives for
Acids), Poly(monothioimidodiphosphonic	monothiohydrazidodiphosphonic acids, where
Acid),	R, R′, R″, and R″′ represent H, NH₂or any
Poly(monothiohydrazidodiphosphonic	organic functional group wherein the number of
Acids), and derivatives thereof (S—O	carbon atoms ranges from 0 to 40, optionally
Bidentates, S—O Tridentates, S—O	having halogen or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #12:	(RR′—N—)(R″—)P(═S)—NH—P(═O)(—R″′)(—N—
Monothioimidodiphosphonamides,	R″″R″″′) for monothioimidodiphosphonamides,
Monothiohydrazidodiphosphonamides,	and —NH—NH—derivatives for
Bis(monothioimidodiphosphonamides),	monothiohydrazidodiphosphonamides, where R,
Bis(monothiohydrazidodiphosphonamidcs)	R′, R″, R″′, R″″, and R″″′, represent H, NH₂or
Poly(monothioimidodiphosphonamides),	any organic functional group wherein the
and	number of carbon atoms ranges from 0 to 40,
Poly(monothiohydrazidodiphosphonamides)	optionally having halogen or polarizing or
(S—O Bidentates, S—O Tridentates, S—O	water-insolubilizing/solubilizing groups
Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S—O Valence Stabilizer #13:	(RR′—N—)(R″—)P(═S)—S—P(═O)(—R″′)(—N—
Monothiodiphosphonamides,	R″″R″″′), or (RR′—N—)(R″—)P(═S)—O—P(═O)(—
Bis(monothioiphosphonarnides), and	R″′)(—N—R″″R″″′), where R, R′, R″, R″′, R″″,
Poly(monothiodiphosphonamides) (S—O	and R″″′ represent H, NH₂or any organic
Bidentates, S—O Tridentates, S—O	functional group wherein the number of carbon
Tetradentates)	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #14:	(R—O—)(R′—)P(═S)—O—P(═O)(—R″)(—O—R″′); (R—
Monothiodiphosphonic Acids,	O—)(R′—)P(═S)—S—P(═O)(—R″)(—O—R″′); (R—S—)
Bis(monothioiphosphonic Acids),	(R′—)P(═S)—O—P(═O)(—R″)(—S—R″′); or (R—S—)
Poly(monothiodiphosphonic Acids), and	(R′—)P(═S)—S—P(═O)(—R″)(—S—R″′), where R,
derivatives thereof (S—O Bidentates, S—O	R′, R″, and R″′ represent H, NH₂or any organic
Tridentates, S—O Tetradentates)	functional group wherein the number of carbon
	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #15:	(RR′—N—)(R″—)P(═S)—S—S—P(═O)(—R″′)(—N—
Monothioperoxydiphosphonamide,	R″″R″″′), where R, R′, R″, R″′, R″″, and R″″′
Bis(monothioperoxyphosphonamide), and	represent H, NH₂or any organic functional
Poly(monothioperoxydiphosphonamide) (S—O	group wherein the number of carbon atoms
Bidentates, S—O Tridentates, S—O	ranges from 0 to 40, optionally having halogen
Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #16:	(R—O—)(R′—)P(═S)—S—S—P(═O)(—R″)(—O—R″′); or
Monothioperoxydiphosphonic Acids,	(R—S—)(R′—)P(═S)—S—S—P(═O)(—R″)(—S—R″′),
Bis(monothioperoxyphosphonic Acids),	where R, R′, R″, and R″′ represent H, NH₂or
Poly(monothioperoxydiphosphonic Acids),	any organic functional group wherein the
and derivatives thereof (S—O Bidentates, S—O	number of carbon atoms ranges from 0 to 40,
Tridentates, S—O Tetradentates)	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S—O Valence Stabilizer #17:	(O═)P(—S—R)(—O—R′)(—O—R″) or (S═)P(—O—R)(—O—
Monothiophosphoric Acids	R′)(—O—R″), where R, R′, and R″ represent H,
(Phosphorothioic Acids),	NH₂or any organic functional group wherein
Bis(monothiophosphoric acids),	the number of carbon atoms ranges from 0 to
Poly(monothiophosphoric acids), and	40, optionally having halogen or polarizing or
derivatives thereof (S—O Bidentates, S—O	water-insolubilizing/solubilizing groups
Tridentates, S—O Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S—O Valence Stabilizer #18:	(O═)P(—S—S—R)(—O—R′)(—O—R″), where R, R′,
Phosphoro(dithioperoxoic) Acids,	and R″ represent H, NH₂or any organic
Bis[phosphoro(dithioperoxoic) acids],	functional group wherein the number of carbon
Poly[phosphoro(dithioperoxoic) acids], and	atoms ranges from 0 to 40, optionally having
derivatives thereof (S—O Bidentates, S—O	halogen or polarizing or water-
Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #19:	(O═)PR(—S—R′)(—O—R″) or (S═)PR(—O—R′)(—O—
Monothiophosphonic Acids	R″), where R, R′, and R″ represent H, NH₂or
(Phosphonothioic Acids),	any organic functional group wherein the
Bis(monothiophosphonic Acids),	number of carbon atoms ranges from 0 to 40,
Poly(monothiophosphonic Acids), and	optionally having halogen or polarizing or
derivatives thereof (S—O Bidentates, S—O	water-insolubilizing/solubilizing groups
Tridentates, S—O Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S—O Valence Stabilizer #20:	(O═)PR(—S—S—R′)(—O—R″), where R, R′, and R″
Phosphono(dithioperoxoic) Acids,	represent H, NH₂or any organic functional
Bis[phosphono(dithioperoxoic) Acids],	group wherein the number of carbon atoms
Poly[phosphono(dithioperoxoic) Acids],	ranges from 0 to 40, optionally having halogen
and derivatives thereof (S—O Bidentates, S—O	or polarizing or water-
Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #21:	R—CR′(—OH)—CH2—C(═S)—R″, where R, R′, and
Beta-Hydroxythioketones, Beta-	R″ represent H, NH₂or any organic functional
Hydroxythioaldehydes, Bis(beta-	group wherein the number of carbon atoms
hydroxythioketones), Bis(beta-	ranges from 0 to 40, optionally having halogen
hydroxythioaldehydes), Poly(beta-	or polarizing or water-
hydroxythioketones), and Poly(beta-	insolubilizing/solubilizing groups attached.
hydroxythioaldehydes) (S—O Bidentates, S—O	Ligand can also contain nonbinding N, O, S, or
Tridentates, S—O Tetradentates)	P atoms.
S—O Valence Stabilizer #22:	R—CR′(—SH)—CH2—C(═O)—R″, where R, R′, and
Beta-Mercaptoketones, Beta-	R″ represent H, NH₂or any organic functional
Mercaptoaldehydes, Bis(beta-	group wherein the number of carbon atoms
mercaptoketones), Bis(beta-	ranges from 0 to 40, optionally having halogen
mercaptoaldehydes), Poly(beta-	or polarizing or water-
mereaptoketones), and Poly(beta-	insolubilizing/solubilizing groups attached.
mercaptoaldehydes) (S—O Bidentates, S—O	Ligand can also contain nonbinding N, O, S, or
Tridentates, S—O Tetradentates)	P atoms.
S—O Valence Stabilizer #23:	RR′—N—CH(—OH)—NR″—C(═S)—NR″′R″″, where
N-(Aminomethylol)thioureas [N-	R, R′, R″, R″′, and R″″ represent H, NH₂or any
(Aminohydroxymethyl)thioureas], Bis[N-	organic functional group wherein the number of
(aminomethylol)thioureas], and Poly[N-	carbon atoms ranges from 0 to 40, optionally
(aminomethylol)thioureas](S—O Bidentates,	having halogen or polarizing or water-
S—O Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #24:	RR′—N—CH(—SH)—NR″—C(═O)—NR″′R″″, where
N-(Aminomethylthiol)ureas [N-	R, R′, R″, R″′, and R″″ represent H, NH₂or any
(Aminomercaptomethyl)ureas], Bis[N-	organic functional group wherein the number of
(aminomethylthiol)ureas], and Poly[N-	carbon atoms ranges from 0 to 40, optionally
(aminomethylthiol)ureas](S—O Bidentates,	having halogen or polarizing or water-
S—O Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #25:	RR′—N—C(═S)—C(═O)—N—R″R″′, where R, R′,
Monothiooxamides,	R″, and R″′ represent H, NH₂or any organic
Bis(monothiooxamides), and	functional group wherein the number of carbon
Poly(monothiooxamides) (S—O Bidentates,	atoms ranges from 0 to 40, optionally having
S—O Tridentates, S—O Tetradentates)	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #26:	R—CR′(—SH)—CR″R″′—C(═O)(—O—R″″), where R,
Beta-Mercapto Carboxylic Acids, Bis(Beta-	R′, R″, R″′, and R″″ represent H, NH₂or any
Mercapto Carboxylic Acids), Poly(Beta-	organic functional group wherein the number of
Mercapto Carboxylic Acids), and	carbon atoms ranges from 0 to 40, optionally
derivatives thereof (S—O Bidentates, S—O	having halogen or polarizing or water-
Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #27:	R—CR′(—SH)—CR″R″′—C(═O)(—S—R″″), where R,
Beta-Mercapto Thiocarboxylic Acids,	R′, R″, R″′, and R″″ represent H, NH₂or any
Bis(Beta-Mercapto Thiocarboxylic Acids),	organic functional group wherein the number of
Poly(Beta-Mercapto Thiocarboxylic Acids),	carbon atoms ranges from 0 to 40, optionally
and derivatives thereof (S—O Bidentates, S—O	having halogen or polarizing or water-
Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #28:	R—CR′(—OH)—CR″R″′—C(═O)(—S—R″″), where R,
Beta-Hydroxy Thiocarboxylic Acids,	R′, R″, R″′, and R″″ represent H, NH₂or any
Bis(Beta-Hydroxy Thiocarboxylic Acids),	organic functional group wherein the number of
Poly(Beta-Hydroxy Thiocarboxylic Acids),	carbon atoms ranges from 0 to 40, optionally
and derivatives thereof (S—O Bidentates, S—O	having halogen or polarizing or water-
Tridentates, S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #29:	R—CR′(—SH)—CR″R″′—C(═O)(—NH—R″″), where
Beta-Mercapto Carboxamides, Bis(Beta-	R, R′, R″, R″′, and R″″ represent H, NH₂or any
Mercapto Carboxamides), Poly(Beta-	organic functional group wherein the number of
Mercapto Carboxamides), and derivatives	carbon atoms ranges from 0 to 40, optionally
thereof (S—O Bidentates, S—O Tridentates,	having halogen or polarizing or water-
S—O Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #30:	R—S—R′COOH for S-alkylthiocarboxylic and S-
S-Alkylthiocarboxylic Acids, S-	arylthiocarboxylic acids, and HOOCR—S—
Arylthiocarboxylic Acids, and S,S-	R′COOH for S,S-thiobiscarboxylic acids, where
thiobiscarboxylic Acids (S—O Bidentates	R and R′ represent H or any organic functional
and S—O Tridentates)	group wherein the number of carbon atoms
	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #31:	R—S—S—R′COOH for S-alkyldisulfidocarboxylic
S-Alkyldisulfidocarboxylic Acids, S-	and S-aryldisulfidocarboxylic acids, and
Aryldisulfidocarboxylic Acids, and S,S′—	HOOCR—S—S—R′COOH for S,S′-
Disulfidobiscarboxylic Acids (S—O	disulfidobiscarboxylic acids, where R and R′
Bidentates and S—O Tridentates)	represent H or any organic functional group
	wherein the number of carbon atoms ranges
	from 0 to 40, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, O, S, or P atoms.
S—O Valence Stabilizer #32:	R—C(═O)(—S—R′) for monothiomonocarboxylic
Monothiomonocarboxylic Acids,	acids, and (R—S—)(O═)C—R′—C(═O)(—S—R″) or (R—
Dithiodicarboxylic Acids,	S—)(O═)C—R′—C(═O)(—O—R″) for
Bis(monothiomonocarboxylic Acids),	dithiodicarboxylic acids, where R, R′, and R″
Bis(dithiodicarboxylic acids),	represent H, NH₂or any organic functional
Poly(monothiomonocarboxylic acids),	group wherein the number of carbon atoms
Poly(dithiodicarboxylic acids), and	ranges from 0 to 40, optionally having halogen
derivatives thereof (S—O Bidentates and S—O	or polarizing or water-
Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #33:	R—O—C(═S)—O—R′, where R, and R′ represent H,
Monothiocarbonates and	NH₂or any organic functional group wherein
Bis(monothiocarbonates) (S—O Bidentates	the number of carbon atoms ranges from 0 to
and S—O Tetradentates)	40, optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S—O Valence Stabilizer #34:	RR′N—NR″—C(═O)(SH), where R and R′
Monothiocarbazates (Monothiocarbazides),	represent H, NH₂or any organic functional
Bis(monothiocarbazates), and	group wherein the number of carbon atoms
Poly(monothiocarbazates) (S—O Bidentates,	ranges from 0 to 40, optionally having halogen
S—O Tridentates, and S—O Tetradentates; or	or polarizing or water-
possibly N—S Bidentates, N—S Tridentates,	insolubilizing/solubilizing groups attached.
and N—S Tetradentates)	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #35:	R—CH(—SH)—CH(—OH)—R′ for alpha-mercapto
Mercapto Alcohols and	alcohols, R—CH(—SH)—Si(—OR′)_x—R″_3-xfor alpha-
Silylmercaptoalcohols, Bis(mercapto	silylmercaptoalcohols, R—CH(—SH)—R′—CH(—
alcohols and silylmercaptoalcohols), and	OH)—R″ for beta-mercapto alcohols, and R—CH(—
Poly(mercapto alcohols and	SH)—R′—Si(—OR″)_x—R″′_3-xfor beta-
silylmercaptoalcohols) (S—O Bidentates, S—O	silylmercaptoalcohols, etc., where R, R′, R″,
Tridentates, S—O Tetradentates)	and R″′ represent H, NH₂or any organic
	functional group wherein the number of carbon
	atoms ranges from 0 to 40, optionally having
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached. x = 1-3.
	Ligand can also contain nonbinding N, O,
	S, or P atoms.
S—O Valence Stabilizer #36:	RN═C(OH)(SH), where R represents H, NH₂or
Monothiocarbimates,	any organic functional group wherein the
Bis(monothiocarbimates), and	number of carbon atoms ranges from 0 to 40,
Poly(monothiocarbimates) (S—O Bidentates,	optionally having halogen or polarizing or
S—O Tridentates, and S—O Tetradentates)	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
S—O Valence Stabilizer #37:	R—O—C(—S—R″)—O—R′, where R, R′, and R″
Alkyl-and Aryl-Monothioborates and	represent H, NH₂or any organic functional
Bis(monothioborates) (S—O Bidentates and	group wherein the number of carbon atoms
S—O Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #38:	R—C(—S—R″)—O—R′, where R, R′, and R″
Alkyl-and Aryl-Monothioboronates and	represent H, NH₂or any organic functional
Bis(monothioboronates) (S—O Bidentates	group wherein the number of carbon atoms
and S—O Tetradentates)	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #39:	(O═)As(—S—R)(—O—R′)(—O—R″) or (S═)As(—O—
Monothioarsonic Acids (Arsonothioic	R)(—O—R′)(—O—R″), where R, R′, and R″
Acids), Bis(monothioarsonic acids),	represent H, NH₂or any organic functional
Poly(monothioarsonic acids), and	group wherein the number of carbon atoms
derivatives thereof (S—O Bidentates, S—O	ranges from 0 to 40, optionally having halogen
Tridentates, S—O Tetradentates)	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
S—O Valence Stabilizer #40:	Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two	sulfur atoms. In addition, ligand contains
Sulfur Atoms at least one additional	additional oxygen-containing substituents
Oxygen Atom Binding Site not in a Ring	(usually hydroxy, carboxy, or carbonyl groups)
(S—O Bidentates, S—O Tridentates, S—O	that constitute O binding sites. Can include
Tetradentates, or S—O Hexadentates)	other ring systems bound to the heterocyclic
	ring or to the O-containing substituent, but they
	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	N, P, As or Se atoms. This 5-membered ring(s)
	and/or attached, uncoordinating rings and/or O-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S—O Valence Stabilizer #41:	Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two	oxygen atoms. In addition, ligand contains
Oxygen Atoms at least one additional	additional sulfur-containing substituents
Sulfur Atom Binding Site not in a Ring (S—O	(usually thio, mercapto, or thiocarbonyl groups)
Bidentates, S—O Tridentates, S—O	that constitute S binding sites. Can include
Tetradentates, or S—O Hexadentates)	other ring systems bound to the heterocyclic
	ring or to the S-containing substituent, but they
	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	N, P, As or Se atoms. This 5-membered ring(s)
	and/or attached, uncoordinating rings and/or S-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S—O Valence Stabilizer #42:	Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two	sulfur atoms. In addition, ligand contains
Sulfur Atoms at least one additional	additional oxygen-containing rings that
Oxygen Atom Binding Site in a separate	constitute O binding sites. Can include other
Ring (S—O Bidentates, S—O Tridentates, S—O	ring systems bound to the O-containing
Tetradentates, or S—O Hexadentates)	heterocyclic rings, but they do not coordinate
	with the stabilized, high valence metal ion.
	Ring(s) can also contain O, N, P, As, or Se
	atoms. This 5-membered ring(s) and/or
	additional O-containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S—O Valence Stabilizer #43:	Macrocyclic ligands containing two to ten sulfur
Two-, Three-, Four-, Five-, Six-, Seven-,	or oxygen binding sites to valence stabilize the
Eight-, Nine-, and Ten-Membered	central metal ion. Can include other
Macrocyclics, Macrobicyclics, and	hydrocarbon or ring systems bound to this
Macropolycyclics (including Catapinands,	macrocyclic ligand, but they do not coordinate
Cryptands, Cyclidenes, and Sepulchrates)	with the stabilized, high valence metal ion. This
wherein all Binding Sites are composed of	ligand and/or attached, uncoordinating
Sulfur (usually thiol, mercapto, or	hydrocarbons/rings may or may not have
thiocarbonyl groups) or Oxygen (hydroxy,	halogen or polarizing or water-
carboxy, or carbonyl groups) and are not	insolubilizing/solubilizing groups attached.
contained in Component Heterocyclic
Rings (S—O Bidentates, S—O Tridentates, S—O
Tetradentates, and S—O Hexadentates)
S—O Valence Stabilizer #44:	Macrocyclic ligands containing a total of four to
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	ten five-membered heterocyclic rings containing
Ten-Membered Macrocyclics,	sulfur or oxygen binding sites. Can include
Macrobicyclics, and Macropolycyclics	other hydrocarbon/ring systems bound to this
(including Catapinands, Cryptands,	macrocyclic ligand, but they do not coordinate
Cyclidenes, and Sepulchrates) wherein all	with the stabilized, high valence metal ion. This
Binding Sites are composed of Sulfur or	ligand and/or attached, uncoordinating
Oxygen and are contained in Component 5-	hydrocarbon/rings may or may not have halogen
Membered Heterocyclic Rings (S—O	or polarizing or water-insolubilizing groups
Tridentates, S—O Tetradentates or S—O	attached.
Hexadentates)
S—O Valence Stabilizer #45:	Macrocyclic ligands containing at least one
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	heterocyclic ring. These heterocyclic rings
Ten-Membered Macrocyclics,	provide sulfur or oxygen binding sites to
Macrobicyclics, and Macropolycyclics	valence stabilize the central metal ion. Other
(including Catapinands, Cryptands,	thiol, mercapto, thiocarbonyl, hydroxy, carboxy,
Cyclidenes, and Sepulchrates) wherein all	or carbonyl binding sites can also be included in
Binding Sites are composed of Sulfur or	the macrocyclic ligand, so long as the total
Oxygen and are contained in a Combination	number of binding sites is four to ten. Can
of Heterocyclic Rings and Thiol, Mercapto,	include other hydrocarbon/ring systems bound
Thiocarbonyl, Hydroxy, Carboxy, and	to this macrocyclic ligand, but they do not
Carbonyl Groups (S—O Tridentates, S—O	coordinate with the stabilized, high valence
Tetradentates, or S—O Hexadentates)	metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
S—O Valence Stabilizer #46:	Sulfoxides (R—SO—R′), where R and R′
Sulfoxides (S—O Bidentates)	represent H or any organic functional group
	wherein the number of carbon atoms ranges
	from 0 to 35, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached.
S—O Valence Stabilizer #47:	Sulfones (R—SO₂—R′), where R and R′ represent
Sulfones (S—O Bidentates)	H or any organic functional group wherein the
	number of carbon atoms ranges from 0 to 35,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached.
S—O Valence Stabilizer #48:	Sulfur dioxide ligands (—SO₂) bound directly to
Sulfur dioxide (SO₂) ligands (S—O	the high valence metal ion.
Bidentates)
N—P Valence Stabilizer #1:	[R(—NR′R″)(—PR″′R″″)], [R(—NR′R″)_x]_1-3P, [R
Aminoaryl Phosphines and Iminoaryl	(—NR′R″)_x]_1-3PX, or [R(—PR′R″)_x]_1-3N, where X = O
Phosphines (N—P Bidentates, N—P	or S and R, R′, R″, R″′, and R″″ represents
Tridentates, and N—P Tetradentates)	H, NH₂or any organic functional group wherein
	the number of carbon atoms ranges from 0 to
	35, optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, O, S, or Se atoms.
N—P Valence Stabilizer #2:	Five membered heterocyclic ring(s) containing
Heterocyclic Rings containing One, Two,	one, two, three, or four nitrogen atoms. In
Three, or Four Nitrogen Atoms at least one	addition, ligand contains additional phosphorus-
additional Phosphorus Atom Binding Site	containing substituents that constitute P binding
not in a Ring (N—P Bidentates, N—P	sites. Can include other ring systems bound to
Tridentates, N—P Tetradentates, or N—P	the heterocyclic ring or to the P-containing
Hexadentates)	substituent, but they do not coordinate with the
	stabilized, high valence metal ion. Ring(s) can
	also contain O, S, or P atoms. This ring(s)
	and/or attached, uncoordinating rings and/or P-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—P Valence Stabilizer #3:	Five membered heterocyclic ring(s) containing
Heterocyclic Rings containing One, Two,	one, two, or three phosphorus atoms. In
or Three Phosphorus Atoms at least one	addition, ligand contains additional nitrogen-
additional Nitrogen Atom Binding Site not	containing substituents (usually amines, imines,
in a Ring (N—P Bidentates, N—P Tridentates,	or hydrazides) that constitute N binding sites.
N—P Tetradentates, or N—P Hexadentates)	Can include other ring systems bound to the
	heterocyclic ring or to the N-containing
	substituent, but they do not coordinate with the
	stabilized, high valence metal ion. Ring(s) can
	also contain O, S, or P atoms. This ring(s)
	and/or attached, uncoordinating rings and/or N-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—P Valence Stabilizer #4:	Heterocyclic ring(s) containing one, two, three,
Heterocyclic Rings containing One, Two,	or four nitrogen atoms. In addition, ligand
Three, or Four Nitrogen Atoms at least one	contains additional phosphorus-containing rings
additional Phosphorus Atom Binding Site	that constitute P binding sites. Can include
in a Separate Ring (N—P Bidentates, N—P	other ring systems bound to the N- or P-
Tridentates, N—P Tetradentates)	containing heterocyclic rings, but they do not
	coordinate with the stabilized, high valence
	metal ion. Ring(s) can also contain O, S, or P
	atoms. This ring(s) and/or additional P-
	containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
N—P Valence Stabilizer #5:	Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Five-, Six-, Seven-,	five, six, seven, eight, nine, or ten binding sites
Eight-, Nine-, and Ten-Membered	composed of nitrogen and phosphorus to
Macrocyclics, Macrobicyclics, and	valence stabilize the central metal ion. Can
Macropolycyclics (including Catapinands,	include other hydrocarbon or ring systems
Cryptands, Cyclidenes, and Sepulchrates)	bound to this macrocyclic ligand, but they do
wherein all Binding Sites are composed of	not coordinate with the stabilized, high valence
Nitrogen (usually amine or imine groups) or	metal ion. This ligand and/or attached,
Phosphorus and are not contained in	uncoordinating hydrocarbons/rings may or may
Component Heterocyclic Rings (N—P	not have halogen or polarizing or water-
Bidentates, N—P Tridentates, N—P	insolubilizing/solubilizing groups attached.
Tetradentates, and N—P Hexadentates)
N—P Valence Stabilizer #6:	Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	five, six, seven, eight, nine, or ten heterocyclic
Ten-Membered Macrocyclics,	rings containing nitrogen or phosphorus binding
Macrobicyclics, and Macropolycyclics	sites. Can include other hydrocarbon/ring
(including Catapinands, Cryptands,	systems bound to this macrocyclic ligand, but
Cyclidenes, and Sepulchrates) wherein all	they do not coordinate with the stabilized, high
Binding Sites are composed of Nitrogen or	valence metal ion. This ligand and/or attached,
Phosphorus and are contained in	uncoordinating hydrocarbon/rings may or may
Component Heterocyclic Rings (N—P	not have halogen or polarizing or water-
Bidentates, N—P Tridentates, N—P	insolubilizing groups attached.
Tetradentates, or N—P Hexadentates)
N—P Valence Stabilizer #7:	Macrocyclic ligands containing at least one
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	heterocyclic ring. These heterocyclic rings
Ten-Membered Macrocyclics,	provide nitrogen or phosphorus binding sites to
Macrobicyclics, and Macropolycyclics	valence stabilize the central metal ion. Other
(including Catapinands, Cryptands,	amine, imine, or phosphine binding sites can
Cyclidenes, and Sepulchrates) wherein all	also be included in the macrocyclic ligand, so
Binding Sites are composed of Nitrogen or	long as the total number of binding sites is four,
Phosphorus and are contained in a	five, six, seven, eight, nine, or ten. Can include
Combination of Heterocyclic Rings and	other hydrocarbon/ring systems bound to this
Amine, Imine, and Phosphine Groups (N—P	macrocyclic ligand, but they do not coordinate
Bidentates, N—P Tridentates, N—P	with the stabilized, high valence metal ion. This
Tetradentates, or N—P Hexadentates)	ligand and/or attached, uncoordinating
	hydrocarbon/rings may or may not have halogen
	or polarizing or water-insolubilizing groups
	attached.
S—P Valence Stabilizer #1:	[R(—SR′)_x]_1-3P, [R(—SR′)_x]_1-3PX, [R(—PR′R″)
Thioaryl Phosphines (S—P Bidentates, S—P	(—SR″′)], [R(—PR′R″)(—S—S—R″′)], [R(—PR′R″)
Tridentates, and S—P Tetradentates)	(—C(═S)R″′], [R(—PR′R″)_x]₂S, [R(—PR′R″)_x]_2-3
	R″′(—SR″′)_y, [R(—SR′)_x]_2-3R″(—PR″′R″″)_y, [R(—
	PR′R″)_x]₂S₂, and [R(—PR′R″)_x]₂R″′(C(═S))_yR″″,
	where X = O or S, and R, R′, R″, R″′, and R″″
	represent H, NH_2,or any organic functional
	group wherein the number of carbon atoms
	ranges from 0 to 40, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached, and
	x = 1-2 and y = 1-4. Ligand can also contain
	nonbinding N, O, S, or P atoms.
S—P Valence Stabilizer #2:	Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two	sulfur atoms. In addition, ligand contains
Sulfur Atoms at least one additional	additional phosphorus-containing substituents
Phosphorus Atom Binding Site not in a	that constitute P binding sites. Can include
Ring (P—S Bidentates, P—S Tridentates, P—S	other ring systems bound to the heterocyclic
Tetradentates, or P—S Hexadentates)	ring or to the P-containing substituent, but they
	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	S, or P atoms. This ring(s) and/or attached,
	uncoordinating rings and/or P-containing
	substituent(s) may or may not have halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached.
S—P Valence Stabilizer #3:	Heterocyclic ring(s) containing one, two, or
Heterocyclic Rings containing One, Two,	three phosphorus atoms. In addition, ligand
or Three Phosphorus Atoms at least one	contains additional sulfur-containing
additional Sulfur Atom Binding Site not in	substituents (usually thiol, mercapto, or
a Ring (S—P Bidentates, S—P Tridentates, S—P	thiocarbonyl groups) that constitute S binding
P Tetradentates, or S—P Hexadentates)	sites. Can include other ring systems bound to
	the heterocyclic ring or to the S-containing
	substituent, but they do not coordinate with the
	stabilized, high valence metal ion. Ring(s) can
	also contain O, S, or P atoms. This ring(s)
	and/or attached, uncoordinating rings and/or S-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S—P Valence Stabilizer #4:	Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two	sulfur atoms. In addition, ligand contains
Sulfur Atoms at least one additional	additional phosphorus-containing rings that
Phosphorus Atom Binding Site in a	constitute P binding sites. Can include other
Separate Ring (S—P Bidentates, S—P	ring systems bound to the S- or P-containing
Tridentates, S—P Tetradentates)	heterocyclic rings, but they do not coordinate
	with the stabilized, high valence metal ion.
	Ring(s) can also contain O, S, or P atoms. This
	ring(s) and/or additional P-containing ring(s)
	and/or attached, uncoordinating rings may or
	may not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
S—P Valence Stabilizer #5:	Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Five-, Six-, Seven-,	five, six, seven, eight, nine, or ten binding sites
Eight-, Nine-, and Ten-Membered	composed of sulfur and phosphorus to valence
Macrocyclics, Macrobicyclics, and	stabilize the central metal ion. Can include other
Macropolycyclics (including Catapinands,	hydrocarbon or ring systems bound to this
Cryptands, Cyclidenes, and Sepulchrates)	macrocyclic ligand, but they do not coordinate
wherein all Binding Sites are composed of	with the stabilized, high valence metal ion. This
Sulfur (usually thiol, mercapto, or	ligand and/or attached, uncoordinating
thiocarbonyl groups) or Phosphorus and are	hydrocarbons/rings may or may not have
not contained in Component Heterocyclic	halogen or polarizing or water-
Rings (S—P Bidentates, S—P Tridentates, S—P	insolubilizing/solubilizing groups attached.
Tetradentates, and S—P Hexadentates)
S—P Valence Stabilizer #6:	Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	five, six, seven, eight, nine, or ten heterocyclic
Ten-Membered Macrocyclics,	rings containing sulfur or phosphorus binding
Macrobicyclics, and Macropolycyclics	sites. Can include other hydrocarbon/ring
(including Catapinands, Cryptands,	systems bound to this macrocyclic ligand, but
Cyclidenes, and Sepulchrates) wherein all	they do not coordinate with the stabilized, high
Binding Sites are composed of Sulfur or	valence metal ion. This ligand and/or attached,
Phosphorus and are contained in	uncoordinating hydrocarbon/rings may or may
Component Heterocyclic Rings (S—P	not have halogen or polarizing or water-
Bidentates, S—P Tridentates, S—P	insolubilizing groups attached.
Tetradentates, or S—P Hexadentates)
S—P Valence Stabilizer #7:	Macrocyclic ligands containing at least one
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	heterocyclic ring. These heterocyclic rings
Ten-Membered Macrocyclics,	provide sulfur or phosphorus binding sites to
Macrobicyclics, and Macropolycyclics	valence stabilize the central metal ion. Other
(including Catapinands, Cryptands,	thiol, mercapto, or thiocarbonyl, or phosphine
Cyclidenes, and Sepulchrates) wherein all	binding sites can also be included in the
Binding Sites are composed of Sulfur or	macrocyclic ligand, so long as the total number
Phosphorus and are contained in a	of binding sites is four, five, six, seven, eight,
Combination of Heterocyclic Rings and	nine, or ten. Can include other
Thiol, Mercapto, Thiocarbonyl or	hydrocarbon/ring systems bound to this
Phosphine Groups (S—P Bidentates, S—P	macrocyclic ligand, but they do not coordinate
Tridentates, S—P Tetradentates, or S—P	with the stabilized, high valence metal ion. This
Hexadentates)	ligand and/or attached, uncoordinating
	hydrocarbon/rings may or may not have halogen
	or polarizing or water-insolubilizing groups
	attached.
P—O Valence Stabilizer #1:	[R(—OR′)_x]_1-3P, [R(—OR′)_x]_1-3PX, [R(—PR′R″(—
Hydroxyaryl Phosphines (P—O Bidentates,	OR″′)], [R(—PR′R″)(—C(═O)R″′], [R(—
P—O Tridentates, and P—O Tetradentates)	PR′R″)_x]₂O, [R(—PR′R″)_x]_2-3R″′(—OR″″)_y, [R(—
	OR′)_x]_2-3R″(—PR″′R″″)_y, and [R(—
	PR′R″)_x]₂R″′(C(═O))_yR″″, where X = O or S,
	and R, R′, R″,and R″′, and R″″ represent H, NH_2,
	or any organic functional group wherein the
	number of carbon atoms ranges from 0 to 40,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached, and x = 1-2 and y = 1-4. Ligand can
	also contain nonbinding N, O, S, or P atoms.
P—O Valence Stabilizer #2:	Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two	oxygen atoms. In addition, ligand contains
Oxygen Atoms at least one additional	additional phosphorus-containing substituents
Phosphorus Atom Binding Site not in a	that constitute P binding sites. Can include
Ring (P—O Bidentates, P—O Tridentates, P—O	other ring systems bound to the heterocyclic
Tetradentates, or P—O Hexadentates)	ring or to the P-containing substituent, but they
	do not coordinate with the stabilized, high
	valence metal ion. Ring(s) can also contain O,
	S, or P atoms. This ring(s) and/or attached,
	uncoordinating rings and/or P-containing
	substituent(s) may or may not have halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached.
P—O Valence Stabilizer #3:	Heterocyclic ring(s) containing one, two, or
Heterocyclic Rings containing One, Two,	three phosphorus atoms. In addition, ligand
or Three Phosphorus Atoms at least one	contains additional oxygen-containing
additional Oxygen Atom Binding Site not	substituents (usually hydroxy, carboxy, or
in a Ring (P—O Bidentates, P—O Tridentates,	carbonyl groups) that constitute O binding sites.
P—O Tetradentates, or P—O Hexadentates)	Can include other ring systems bound to the
	heterocyclic ring or to the O-containing
	substituent, but they do not coordinate with the
	stabilized, high valence metal ion. Ring(s) can
	also contain O, S, or P atoms. This ring(s)
	and/or attached, uncoordinating rings and/or O-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P—O Valence Stabilizer #4:	Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two	oxygen atoms. In addition, ligand contains
Oxygen Atoms at least one additional	additional phosphorus-containing rings that
Phosphorus Atom Binding Site in a	constitute P binding sites. Can include other
Separate Ring (P—O Bidentates, P—O	ring systems bound to the O- or P-containing
Tridentates, P—O Tetradentates)	heterocyclic rings, but they do not coordinate
	with the stabilized, high valence metal ion.
	Ring(s) can also contain O, S, or P atoms. This
	ring(s) and/or additional P-containing ring(s)
	and/or attached, uncoordinating rings may or
	may not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
P—O Valence Stabilizer #5:	Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Five-, Six-, Seven-,	five, six, seven, eight, nine, or ten binding sites
Eight-, Nine-, and Ten-Membered	composed of oxygen and phosphorus to valence
Macrocyclics, Macrobicyclics, and	stabilize the central metal ion. Can include other
Macropolycyclics (including Catapinands,	hydrocarbon or ring systems bound to this
Cryptands, Cyclidenes, and Sepulchrates)	macrocyclic ligand, but they do not coordinate
wherein all Binding Sites are composed of	with the stabilized, high valence metal ion. This
Oxygen (usually hydroxy, carboxy, or	ligand and/or attached, uncoordinating
carbonyl groups) or Phosphorus and are not	hydrocarbons/rings may or may not have
contained in Component Heterocyclic	halogen or polarizing or water-
Rings (P—O Bidentates, P—O Tridentates, P—O	insolubilizing/solubilizing groups attached.
Tetradentates, and P—O Hexadentates)
P—O Valence Stabilizer #6:	Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	five, six, seven, eight, nine, or ten heterocyclic
Ten-Membered Macrocyclics,	rings containing oxygen or phosphorus binding
Macrobicyclics, and Macropolycyclics	sites. Can include other hydrocarbon/ring
(including Catapinands, Cryptands,	systems bound to this macrocyclic ligand, but
Cyclidenes, and Sepulchrates) wherein all	they do not coordinate with the stabilized, high
Binding Sites are composed of Oxygen or	valence metal ion. This ligand and/or attached,
Phosphorus and are contained in	uncoordinating hydrocarbon/rings may or may
Component Heterocyclic Rings (P—O	not have halogen or polarizing or water-
Bidentates, P—O Tridentates, P—O	insolubilizing groups attached.
Tetradentates, or P—O Hexadentates)
P—O Valence Stabilizer #7:	Macrocyclic ligands containing at least one
Four-, Five-, Six-, Seven-, Eight-, Nine-, or	heterocyclic ring. These heterocyclic rings
Ten-Membered Macrocyclics,	provide oxygen or phosphorus binding sites to
Macrobicyclics, and Macropolycyclics	valence stabilize the central metal ion. Other
(including Catapinands, Cryptands,	hydroxy, carboxy, carbonyl, or phosphine
Cyclidenes, and Sepulchrates) wherein all	binding sites can also be included in the
Binding Sites are composed of Oxygen or	macrocyclic ligand, so long as the total number
Phosphorus and are contained in a	of binding sites is four, five, six, seven, eight,
Combination of Heterocyclic Rings and	nine, or ten. Can include other
Hydroxy, Carboxy, Carbonyl or Phosphine	hydrocarbon/ring systems bound to this
Groups (P—O Bidentates, P—O Tridentates,	macrocyclic ligand, but they do not coordinate
P—O Tetradentates, or P—O Hexadentates)	with the stabilized, high valence metal ion. This
	ligand and/or attached, uncoordinating
	hydrocarbon/rings may or may not have halogen
	or polarizing or water-insolubilizing groups
	attached.
As Valence Stabilizer #1:	AsH₃, AsH₂R, AsHR₂, where R represents H or
Monoarsines (As Monodentates) wherein at	any organic functional group wherein the
least one Arsenic Atom is a Binding Site	number of carbon atoms ranges from 0 to 25,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, As, O, S, or Se atoms.
As Valence Stabilizer #2:	R′—As—R—As—R″, where R, R′, and R″ represent
Diarsines (an As—As Bidentate) wherein at	H or any organic functional group wherein the
least one Arsenic Atom is a Binding Site	number of carbon atoms ranges from 0 to 25,
	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, As, O, S, or Se atoms.
As Valence Stabilizer #3:	R—As—R′—As—R″—As—R″′, where R, R′, R″, and
Triarsines (either As—As Bidentates or As—	R″′ represent H or any organic functional group
As Tridentates) wherein at least one	wherein the number of carbon atoms ranges
Arsenic Atom is a Binding Site	from 0 to 25, optionally having halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached. Ligand can also contain
	nonbinding N, P, As, O, S, or Se atoms.
As Valence Stabilizer #4:	R—As—R′—As—R″—As—R″′—As—R″″, where R, R′,
Tetraarsines (As—As Bidentates, As—As	R″, R″′, and R″″ represent H or any organic
Tridentates, or As—As Tetradentates)	functional group wherein the number of carbon
wherein at least one Arsenic Atom is a	atoms ranges from 0 to 25, optionally having
Binding Site	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, As, O,
	S, or Se atoms.
As Valence Stabilizer #5:	R—As—R′—As—R″—As—R″′—As—R″″—As—R″″′,
Pentaarsines (As—As Bidentates, As—As	where R, R′, R″, R″′, R″″, and R″″′ represent H
Tridentates, or As—As Tetradentates)	or any organic functional group wherein the
wherein at least one Arsenic Atom is a	number of carbon atoms ranges from 0 to 25,
Binding Site	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, As, O, S, or Se atoms.
As Valence Stabilizer #6:	R—As—R′—As—R″—As—R″′—As—R″″—As—R″″′—As—
Hexaarsines (As—As Bidentates, As—As	R″″″, where R, R′, R″, R″′, R″″, R″″′, and
Tridentates, As—As Tetradentates, or As—As	R″″″ represent H or any organic functional
Hexadentates) wherein at least one Arsenic	group wherein the number of carbon atoms
Atom is a Binding Site	ranges from 0 to 25, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, As, O,
	S, or Se atoms.
As Valence Stabilizer #7:	Five membered heterocyclic ring containing just
Five-Membered Heterocyclic Rings	one arsenic binding site. Can include other ring
containing One Arsenic Atom wherein the	systems bound to this heterocyclic ring, but they
Arsenic Atom is the Binding Site (As	do not coordinate with the stabilized, high
Monodentates)	valence metal ion. Ring can also contain O, S,
	N, P, or Se atoms. This 5-membered ring
	and/or attached, uncoordinating rings may or
	may not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
As Valence Stabilizer #8:	Six membered heterocyclic ring containing just
Six-Membered Heterocyclic Rings	one arsenic binding site. Can include other ring
containing One Arsenic Atom wherein the	systems bound to this heterocyclic ring, but they
Arsenic Atom is the Binding Site (As	do not coordinate with the stabilized, high
Monodentates)	valence metal ion. Ring can also contain O, S,
	N, P, or Se atoms. This 6-membered ring
	and/or attached, uncoordinating rings may or
	may not have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
As Valence Stabilizer #9:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one arsenic atom. In addition, ligand contains
containing One Arsenic Atom and having at	additional arsenic-containing substituents
least one additional Arsenic Atom Binding	(usually arsines) that constitute As binding sites.
Site not in a Ring (As Monodentates, As—As	Can include other ring systems bound to the
Bidentates, As—As Tridentates, As—As	heterocyclic ring or to the As-containing
Tetradentates, or As—As Hexadentates)	substituent, but they do not coordinate with the
	stabilized, high valence metal ion. Ring(s) can
	also contain O, N, S, P or Se atoms. This 5-
	membered ring(s) and/or attached,
	uncoordinating rings and/or As-containing
	substituent(s) may or may not have halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached.
As Valence Stabilizer #10:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one arsenic atom. In addition, ligand contains
containing One Arsenic Atom and having at	additional arsenic-containing substituents
least one additional Arsenic Atom Binding	(usually arsines) that constitute As binding sites.
Site not in a Ring (As Monodentates, As—As	Can include other ring systems bound to the
Bidentates, As—As Tridentates, As—As	heterocyclic ring or to the As-containing
Tetradentates, or As—As Hexadentates)	substituent, but they do not coordinate with the
	stabilized, high valence metal ion. Ring(s) can
	also contain O, N, S, P or Se atoms. This 6-
	membered ring(s) and/or attached,
	uncoordinating rings and/or As-containing
	substituent(s) may or may not have halogen or
	polarizing or water-insolubilizing/solubilizing
	groups attached.
As Valence Stabilizer #11:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one arsenic atom. In addition, ligand contains
containing One Arsenic Atom and having at	additional arsenic-containing rings that
least one additional Arsenic Atom Binding	constitute As binding sites. Can include other
Site in a separate Ring (As Monodentates,	ring systems bound to the As-containing
As—As Bidentates, As—As Tridentates, As—	heterocyclic rings, but they do not coordinate
As Tetradentates, or As—As Hexadentates)	with the stabilized, high valence metal ion.
	Ring(s) can also contain O, N, S, P, or Se
	atoms. This 5-membered ring(s) and/or
	additional As-containing ring(s) and/or
	attached, uncoordinating rings may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
As Valence Stabilizer #12:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one arsenic atom. In addition, ligand contains
containing One Arsenic Atom and having at	additional arsenic-containing rings that
least one additional Arsenic Atom Binding	constitute As binding sites. Can include other
Site in a separate Ring (As Monodentates,	ring systems bound to the As-containing
As—As Bidentates, As—As Tridentates, As—	heterocyclic rings, but they do not coordinate
As Tetradentates, or As—As Hexadentates)	with the stabilized, high valence metal ion.
	Ring(s) can also contain O, N, S, P, or Se
	atoms. This 6-membered ring(s) and/or
	additional As-containing ring(s) and/or
	attached, uncoordinating rings may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
As Valence Stabilizer #13:	Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, and Six-Membered	or six arsenic binding sites to valence stabilize
Macrocyclics, Macrobicyclics, and	the central metal ion. Can include other
Macropolycyclics (including Catapinands,	hydrocarbon or ring systems bound to this
Cryptands, Cyclidenes, and Sepulchrates)	macrocyclic ligand, but they do not coordinate
wherein all Binding Sites are composed of	with the stabilized, high valence metal ion. This
Arsenic and are not contained in	ligand and/or attached, uncoordinating
Component Heterocyclic Rings (As—As	hydrocarbons/rings may or may not have
Bidentates, As—As Tridentates, As—As	halogen or polarizing or water-
Tetradentates, and As—As Hexadentates)	insolubilizing/solubilizing groups attached.
As Valence Stabilizer #14:	Macrocyclic ligands containing a total of four or
Four-, or Six-Membered Macrocyclics,	six five-membered heterocyclic rings containing
Macrobicyclics, and Macropolycyclics	arsenic binding sites. Can include other
(including Catapinands, Cryptands,	hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Arsenic and	with the stabilized, high valence metal ion. This
are contained in Component 5-Membered	ligand and/or attached, uncoordinating
Heterocyclic Rings (As—As Tridentates, As—	hydrocarbon/rings may or may not have halogen
As Tetradentates, or As—As Hexadentates)	or polarizing or water-insolubilizing groups
	attached.
As Valence Stabilizer #15:	Macrocyclic ligands containing at least one 5-
Four-, or Six-Membered Macrocyclics,	membered heterocyclic ring. These
Macrobicyclics, and Macropolycyclics	heterocyclic rings provide arsenic binding sites
(including Catapinands, Cryptands,	to valence stabilize the central metal ion. Other
Cyclidenes, and Sepulchrates) wherein all	arsine binding sites can also be included in the
Binding Sites are composed of Arsenic and	macrocyclic ligand, so long as the total number
are contained in a Combination of 5-	of binding sites is four or eight. Can include
Membered Heterocyclic Rings and Arsine	other hydrocarbon/ring systems bound to this
Groups (As—As Tridentates, As—As	macrocyclic ligand, but they do not coordinate
Tetradentates, or As—As Hexadentates)	with the stabilized, high valence metal ion. This
	ligand and/or attached, uncoordinating
	hydrocarbon/rings may or may not have halogen
	or polarizing or water-insolubilizing groups
	attached.
As Valence Stabilizer #16:	Macrocyclic ligands containing a total of four or
Four-, or Six-Membered Macrocyclics,	six six-membered heterocyclic rings containing
Macrobicyclics, and Macropolycyclics	arsenic binding sites. Can include other
(including Catapinands, Cryptands,	hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Arsenic and	with the stabilized, high valence metal ion. This
are contained in Component 6-Membered	ligand and/or attached, uncoordinating
Heterocyclic Rings (As—As Tridentates, As—	hydrocarbon/rings may or may not have halogen
As Tetradentates, or As—As Hexadentates)	or polarizing or water-insolubilizing groups
	attached.
As Valence Stabilizer #17:	Macrocyclic ligands containing at least one 6-
Four-, or Six-Membered Macrocyclics,	membered heterocyclic ring. These
Macrobicyclics, and Macropolycyclics	heterocyclic rings provide arsenic binding sites
(including Catapinands, Cryptands,	to valence stabilize the central metal ion. Other
Cyclidenes, and Sepulchrates) wherein all	arsine binding sites can also be included in the
Binding Sites are composed of Arsenic and	macrocyclic ligand, so long as the total number
are contained in a Combination of 6-	of binding sites is four or six. Can include other
Membered Heterocyclic Rings and Arsine	hydrocarbon/ring systems bound to this
Groups (As—As Tridentates, As—As	macrocyclic ligand, but they do not coordinate
Tetradentates, or As—As Hexadentates)	with the stabilized, high valence metal ion. This
	ligand and/or attached, uncoordinating
	hydrocarbon/rings may or may not have halogen
	or polarizing or water-insolubilizing groups
	attached.
Se Valence Stabilizer #1:	SeH₂, SeHR, SeR₂, where R represents H or any
Monoselenoethers (Se Monodentates)	organic functional group wherein the number of
wherein at least one Selenium Atom is a	carbon atoms ranges from 0 to 25, optionally
Binding Site	having halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, O, S,
	or Se atoms.
Se Valence Stabilizer #2:	R—Se—R′—Se—R″, where R, R′, and R″ represents
Diselenoethers (Se—Se Bidentates) wherein	H or any organic functional group wherein the
at least one Selenium Atom is a Binding	number of carbon atoms ranges from 0 to 25,
Site	optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	P, O, S, or Se atoms.
Se Valence Stabilizer #3:	R—Se—R′—Se—R″—Se—R″′, where R, R′, R″, and
Triselenoethers (Se—Se Bidentates or Se—Se	R″′ represents H or any organic functional
Tridentates) wherein at least one Selenium	group wherein the number of carbon atoms
Atom is a Binding Site	ranges from 0 to 25, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, O, S,
	or Se atoms.
Se Valence Stabilizer #4:	R—Se—R′—Se—R″—Se—R″′—Se—R″″, where R,R′,
Tetraselenoethers (Se—Se Bidentates, Se—Se	R″, R″′, and R″″ represents H or any organic
Tridentates, or Se—Se Tetradentates)	functional group wherein the number of carbon
wherein at least one Selenium Atom is a	atoms ranges from 0 to 25, optionally having
Binding Site	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, P, O, S,
	or Se atoms.
Se Valence Stabilizer #5:	Five membered heterocyclic ring containing one
Five-Membered Heterocyclic Rings	or two selenium atoms, both of which may
containing One or Two Selenium Atoms	function as binding sites. Can include other
wherein at least one Selenium Atom is a	ring systems bound to this heterocyclic ring, but
Binding Site (Se Monodentates or Se—Se	they do not coordinate with the stabilized, high
Bidentates)	valence metal ion. Ring can also contain O, N,
	P, As, or S atoms. This 5-membered ring and/or
	attached, uncoordinating rings may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
Se Valence Stabilizer #6:	Six membered heterocyclic ring containing one
Six-Membered Heterocyclic Rings	or two selenium atoms, both of which may
containing One or Two Selenium Atoms	function as binding sites. Can include other
wherein at least one Selenium Atom is a	ring systems bound to this heterocyclic ring, but
Binding Site (Se Monodentates or Se—Se	they do not coordinate with the stabilized, high
Bidentates)	valence metal ion. Ring can also contain O, N,
	P, As, or S atoms. This 5-membered ring and/or
	attached, uncoordinating rings may or may not
	have halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
Se Valence Stabilizer #7:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one selenium atom. In addition, ligand contains
containing One Selenium Atom and having	additional selenium-containing substituents
at least one additional Selenium Atom	(usually selenols or selenoethers) that constitute
Binding Site not in a Ring (Se	Se binding sites. Can include other ring
Monodentates, Se—Se Bidentates, Se—Se	systems bound to the heterocyclic ring or to the
Tridentates, Se—Se Tetradentates, or Se—Se	Se-containing substituent, but they do not
Hexadentates)	coordinate with the stabilized, high valence
	metal ion. Ring(s) can also contain O, N, P, As
	or S atoms. This 5-membered ring(s) and/or
	attached, uncoordinating rings and/or Se-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
Se Valence Stabilizer #8:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one selenium atom. In addition, ligand contains
containing One Selenium Atom and having	additional selenium-containing substituents
at least one additional Selenium Atom	(usually selenols or selenoethers) that constitute
Binding Site not in a Ring (Se	Se binding sites. Can include other ring
Monodentates, Se—Se Bidentates, Se—Se	systems bound to the heterocyclic ring or to the
Tridentates, Se—Se Tetradentates, or Se—Se	Se-containing substituent, but they do not
Hexadentates)	coordinate with the stabilized, high valence
	metal ion. Ring(s) can also contain O, N, P, As
	or S atoms. This 6-membered ring(s) and/or
	attached, uncoordinating rings and/or Se-
	containing substituent(s) may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
Se Valence Stabilizer #9:	Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings	one selenium atom. In addition, ligand contains
containing One Selenium Atom and having	additional selenium-containing rings that
at least one additional Selenium Atom	constitute Se binding sites. Can include other
Binding Site in a separate Ring (Se	ring systems bound to the Se-containing
Monodentates, Se—Se Bidentates, Se—Se	heterocyclic rings, but they do not coordinate
Tridentates, Se—Se Tetradentates, or Se—Se	with the stabilized, high valence metal ion.
Hexadentates)	Ring(s) can also contain O, N, P, As, or S
	atoms. This 5-membered ring(s) and/or
	additional Se-containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
Se Valence Stabilizer #10:	Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings	one selenium atom. In addition, ligand contains
containing One Selenium Atom and having	additional selenium-containing rings that
at least one additional Selenium Atom	constitute Se binding sites. Can include other
Binding Site in a separate Ring (Se	ring systems bound to the Se-containing
Monodentates, Se—Se Bidentates, Se—Se	heterocyclic rings, but they do not coordinate
Tridentates, Se—Se Tetradentates, or Se—Se	with the stabilized, high valence metal ion.
Hexadentates)	Ring(s) can also contain O, N, P, As, or S
	atoms. This 6-membered ring(s) and/or
	additional Se-containing ring(s) and/or attached,
	uncoordinating rings may or may not have
	halogen or polarizing or water-
	insolubilizing/solubilizing groups attached.
Se Valence Stabilizer #11:	Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, or Six-Membered	or six selenium binding sites to valence stabilize
Macrocyclics, Macrobicyclics, and	the central metal ion. Can include other
Macropolycyclics (including Catapinands,	hydrocarbon or ring systems bound to this
Cryptands, Cyclidenes, and Sepulchrates)	macrocyclic ligand, but they do not coordinate
wherein all Binding Sites are composed of	with the stabilized, high valence metal ion. This
Selenium (usually selenol or selenoether	ligand and/or attached, uncoordinating
groups) and are not contained in	hydrocarbons/rings may or may not have
Component Heterocyclic Rings (Se—Se	halogen or polarizing or water-
Bidentates, Se—Se Tridentates, Se—Se	insolubilizing/solubilizing groups attached.
Tetradentates, or Se—Se Hexadentates)
Se Valence Stabilizer #12:	Macrocyclic ligands containing a total of four or
Four-, or Six-Membered Macrocyclics,	six five-membered heterocyclic rings containing
Macrobicyclics, and Macropolycyclics	selenium binding sites. Can include other
(including Catapinands, Cryptands,	hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Selenium	with the stabilized, high valence metal ion. This
and are contained in Component 5-	ligand and/or attached, uncoordinating
Membered Heterocyclic Rings (Se—Se	hydrocarbon/rings may or may not have halogen
Tridentates, Se—Se Tetradentates or Se—Se	or polarizing or water-insolubilizing groups
Hexadentates)	attached.
Se Valence Stabilizer #13:	Macrocyclic ligands containing at least one 5-
Four-, or Six-Membered Macrocyclics,	membered heterocyclic ring. These
Macrobicyclics, and Macropolycyclics	heterocyclic rings provide selenium binding
(including Catapinands, Cryptands,	sites to valence stabilize the central metal ion.
Cyclidenes, and Sepulchrates) wherein all	Other selenol or selenoether binding sites can
Binding Sites are composed of Selenium	also be included in the macrocyclic ligand, so
and are contained in a Combination of 5-	long as the total number of binding sites is four
Membered Heterocyclic Rings and Selenol	or six. Can include other hydrocarbon/ring
or Selenoether Groups (Se—Se Tridentates,	systems bound to this macrocyclic ligand, but
Se—Se Tetradentates, or Se—Se	they do not coordinate with the stabilized, high
Hexadentates)	valence metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
Se Valence Stabilizer #14:	Macrocyclic ligands containing a total of four or
Four-, or Six-Membered Macrocyclics,	six six-membered heterocyclic rings containing
Macrobicyclics, and Macropolycyclics	selenium binding sites. Can include other
(including Catapinands, Cryptands,	hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all	macrocyclic ligand, but they do not coordinate
Binding Sites are composed of Selenium	with the stabilized, high valence metal ion. This
and are contained in Component 6-	ligand and/or attached, uncoordinating
Membered Heterocyclic Rings (Se—Se	hydrocarbon/rings may or may not have halogen
Tridentates, Se—Se Tetradentates, or Se—Se	or polarizing or water-insolubilizing groups
Hexadentates)	attached.
Se Valence Stabilizer #15:	Macrocyclic ligands containing at least one 6-
Four-, or Six-Membered Macrocyclics,	membered heterocyclic ring. These
Macrobicyclics, and Macropolycyclics	heterocyclic rings provide selenium binding
(including Catapinands, Cryptands,	sites to valence stabilize the central metal ion.
Cyclidenes, and Sepulchrates) wherein all	Other selenol or selenoether binding sites can
Binding Sites are composed of Selenium	also be included in the macrocyclic ligand, so
and are contained in a Combination of 6-	long as the total number of binding sites is four
Membered Heterocyclic Rings and Selenol	or six. Can include other hydrocarbon/ring
or Selenoether Groups (Se—Se Tridentates,	systems bound to this macrocylic ligand, but
Se—Se Tetradentates, or Se—Se	they do not coordinate with the stabilized, high
Hexadentates)	valence metal ion. This ligand and/or attached,
	uncoordinating hydrocarbon/rings may or may
	not have halogen or polarizing or water-
	insolubilizing groups attached.
Se Valence Stabilizer #16:	R—C(═Se)—CR′R′—C(═Se)—R″′where R, R′, R″,
1,3-Diselenoketones (Diseleno-beta-	and R″′ represent H, NH₂, or any organic
ketonates), 1,3,5-Triselenoketones, Bis(1,3-	functional group wherein the number of carbon
Diselenoketones), and Poly( 1,3-	atoms ranges from 0 to 40, optionally having
Diselenoketones) (S—S Bidentates, S—S	halogen or polarizing or water-
Tridentates, S—S Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
Se Valence Stabilizer #17:	RR′—C═C(—Se)(—Se), where R and R′represent
1,1-Diselenolates, Bis(1,1-diselenolates),	H, NH₂or any organic functional group wherein
and Poly(1,1-diselenolates) (Se—Se	the number of carbon atoms ranges from 0 to
Bidentates and Se—Se Tetradentates)	40, optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
Se Valence Stabilizer #18:	RR′N⁺═C(SeH)(SeH), where R and R′
Diselenocarbamates,	represent H, OH, SH, OR″(R″═C₁—C₃₀alkyl or
Bis(diselenocarbamates), and	aryl), SR″ (R″═C₁—C₃₀alkyl or aryl), NH₂or
Poly(diselenocarbamates) (including N-	any organic functional group wherein the
hydroxydiselenocarbamates and N—	number of carbon atoms ranges from 0 to 40,
mercaptodiselenocarbamates) (Se—Se	optionally having halogen or polarizing or
Bidentates, Se—Se Tridentates, and Se—Se	water-insolubilizing/solubilizing groups
Tetradentates)	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
Se Valence Stabilizer #19:	(O═)P(—Se—R)(—Se—R′)(—Se—R″) or (Se═)P(—Se—
Triselenophosphoric Acids	R)(—Se—R′)(—O—R″), where R, R′, and R″
(Phosphorotriselenoic Acids),	represent H, NH₂or any organic functional
Bis(triselenophosphoric acids),	group wherein the number of carbon atoms
Poly(triselenophosphoric acids), and	ranges from 0 to 40, optionally having halogen
derivatives thereof (Se—Se Bidentates, Se—Se	or polarizing or water-
Tridentates, Se—Se Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
Se Valence Stabilizer #20:	(O═)P(—Se—R)(—Se—R′)(—O—R″) or (Se═)P(—Se—
Diselenophosphoric Acids	R)(—O—R′)(—O—R″), where R, R′, and R″
(Phosphorodiselenoic Acids),	represent H, NH₂or any organic functional
Bis(diselenophosphoric acids),	group wherein the number of carbon atoms
Poly(diselenophosphoric acids), and	ranges from 0 to 40, optionally having halogen
derivatives thereof (Se—Se Bidentates, Se—Se	or polarizing or water-
Tridentates, Se—Se Tetradentates)	insolubilizing/solubilizing groups attached.
	Ligand can also contain nonbinding N, O, S, or
	P atoms.
Se Valence Stabilizer #21:	(Se═)P(—Se—R)(—Se—R′)(—Se—R″), where R, R′,
Tetraselenophosphoric Acids	and R″ represent H, NH₂or any organic
(Phosphorotetraselenoic Acids),	functional group wherein the number of carbon
Bis(tetraselenophosphoric acids),	atoms ranges from 0 to 40, optionally having
Poly(tetraselenophosphoric acids), and	halogen or polarizing or water-
derivatives thereof (Se—Se Bidentates, Se—Se	insolubilizing/solubilizing groups attached.
Tridentates, Se—Se Tetradentates)	Ligand can also contain nonbinding N, O, S, or
	P atoms.
Se Valence Stabilizer #22:	R—Se—C(═Se)—O—R′ or R—Se—C(═O)—Se—R′ for
Diselenocarbonates, Triselenocarbonates,	diselenocarbonates, and R—Se—C(═Se)—Se—R′ for
Bis(diselenocarbonates), and	triselenocarbonates, where R, and R′ represent
Bis(triselenocarbonates), (Se—Se Bidentates	H, NH₂or any organic functional group wherein
and Se—Se Tetradentates)	the number of carbon atoms ranges from 0 to
	40, optionally having halogen or polarizing or
	water-insolubilizing/solubilizing groups
	attached. Ligand can also contain nonbinding N,
	O, S, or P atoms.
Se Valence Stabilizer #23:	Selenocyanates bound directly to the high
Selenocyanates (Se Monodentates)	valence metal ion.
Se Valence Stabilizer #24:	Selenolates (HSe—R, HSe—R—SeH, etc.), where R
Selenolates (Se Monodentates)	and R′represent H or any organic functional
	group wherein the number of carbon atoms
	ranges from 0 to 35, optionally having halogen
	or polarizing or water-
	insolubilizing/solubilizing groups attached.
Miscellaneous Valence Stabilizer #1:	Dialkenes or bicyclic or tricyclic hydrocarbons
Diene or bicyclic or tricyclic hydrocarbon	bound directly to the high valence metal ion.
ligands
Miscellaneous Valence Stabilizer #2:	Cyanide and cyanate and related ligands bound
Cyanide and related ligands	directly to the high valence metal ion.
Miscellaneous Valence Stabilizer #3:	Carbonyl (—CO) ligands bound directly to the
Carbonyl ligands	high valence metal ion.
Miscellaneous Valence Stabilizer #4:	Halogen (X) atoms bound directly to the high
Halogen ligands	valence metal ion.

N Valence Stabilizer #1a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates or N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pentaazacyclodecane ([10]aneN₅); pentaazacycloundecane ([11]aneN₅); pentaazacyclododecane ([12]aneN₅); pentaazacyclotridecane ([13]aneN₅); pentazaacyclotetradecane ([14]aneN₅); pentaazacyclopentadecane ([15]aneN₅); pentaazacyclodecatriene ([10]trieneN₅); pentaazacycloundecatriene ([11]trieneN₅); pentaazacyclododecatriene ([12 trieneN₅); pentaazacyclotridecatriene ([13]trieneN₅); pentazaacyclotetradecatriene ([14]trieneN₅); and pentaazacyclopentadecatriene ([15]trieneN₅).

N Valence Stabilizer #1b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: heptaazacyclotetradecane ([14]aneN₇); heptaazacyclopentadecane ([15]aneN₇); heptaazacyclohexadecanc ([16]aneN₇); heptaazacycloheptadecane ([17]aneN₇); heptaazacyclooctadecane ([18]aneN₇); heptaazacyclononadecane ([19]aneN₇); heptaazacycloeicosane ([20]aneN₇); heptaazacycloheneicosane ([21] aneN₇); heptaazacyclotetradecatriene ([14]trieneN₇); heptaazacyclopentadecatriene ([15]trieneN₇); heptaazacyclohexadecatriene ([16]trieneN₇); heptaazacycloheptadecatriene ([17]trieneN₇); heptaazacyclooctadecatriene ([18]trieneN₇); heptaazacyclononadecatriene ([19]trieneN₇); heptaazacycloeicosatriene ([20]trieneN₇); and heptaazacycloheneicosatriene ([21]trieneN₇).

N Valence Stabilizer #1c: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for include, but are not limited to: nonaazacyclooctadecane ([18]aneN ₉); nonaazacyclononadecane ([19]aneN₉); nonaazacycloeicosane ([20]aneN₉); nonaazacycloheneicosane ([21]aneN₉); nonaazacyclodocosane ([22]aneN₉); nonaazacyclotricosane ([23]aneN₉); nonaazacyclotetracosane ([24]aneN₉); nonaazacyclopentacosane ([25]aneN₉); nonaazacyclohexacosane ([26]aneN₉); nonaazacycloheptacosane ([27]aneN₉); nonaazacyclooctadecatetradiene ([18]tetradieneN₉); nonaazacyclononadecatetradiene ([19]tetradieneN₉); nonaazacycloeicosatetradiene ([20]tetradieneN₉); nonaazacycloheneicosatetradiene ([21]tetradieneN₉); nonaazacyclodocosatetradiene ([22]tetradieneN₉); nonaazacyclotricosatetradiene ([23]tetradieneN₉); nonaazacyclotetracosatetradiene ([24]tetradieneN₉); nonaazacyclopentacosatetradiene ([25]tetradieneN₉); nonaazacyclohexacosatetradiene ([26]tetradieneN₉); and nonaazacycloheptacosatetradiene ([27]tetradieneN₉).

N Valence Stabilizer #2a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pentaphyrins (pentapyrroles); sapphyrins; smaragdyrins; pentaoxazoles; pentaisooxazoles; pentathiazoles; pentaisothiazoles; pentaazaphospholes; pentaimidazoles; pentapyrazoles; pentaoxadiazoles; pentathiadiazoles; pentadiazaphospholes; pentatriazoles; pentaoxatriazoles; and pentathiatriazoles.

N Valence Stabilizer #2b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: heptaphyrins (heptapyrroles); heptaoxazoles; heptaisooxazoles; heptathiazoles; heptaisothiazoles; heptaazaphospholes; heptaimidazoles; heptapyrazoles; heptaoxadiazoles; heptathiadiazoles; heptadiazaphospholes; heptatriazoles; heptaoxatriazoles; and heptathiatriazoles.

N Valence Stabilizer #3a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates or N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: superphthalocyanine; supernaphthalocyanine; diazapentaphyrins; tetraazapentaphyrins; pentaazapentaphyrins; diazapentapyrazoles; tetraazapentapyrazoles; pentaazapentapyrazoles; diazapentaimidazoles; tetraazapentaimidazoles; and pentaazapentaimidazoles.

N Valence Stabilizer #3b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazabeptaphyrins; tetraazaheptaphyrins; hexaazaheptaphyrins; diazaheptapyrazoles; tetraazaheptapyrazoles; hexaazaheptapyrazoles; diazaheptaimidazoles; tetraazaheptaimidazoles; and hexaazaheptaimidazoles.

N Valence Stabilizer #3c: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include,-but are not limited to: diazanonaphyrins; tetraazanonaphyrins; hexaazanonaphyrins; diazanonapyrazoles; tetraazanonapyrazoles; hexaazanonapyrazoles; diazanonaimidazoles; tetraazanonaimidazoles; and hexaazanonaimidazoles.

N Valence Stabilizer #4a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclopentapyridines; cyclopentaoxazines; cyclopentathiazines; cyclopentaphosphorins; cyclopentaquinolines; cyclopentapyrazines; cyclopentapyridazines; cyclopentapyrimidines; cyclopentaoxadiazines; cyclopentathiadiazines; cyclopentadiazaphosphorins cyclopentaquinoxalines; cyclopentatriazines; cyclopentathiatriazines; and cyclopentaoxatriazines.

N Valence Stabilizer #4b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cycloheptapyridines; cycloheptaoxazines; cycloheptathiazines; cycloheptaphosphorins; cycloheptaquinolines; cycloheptapyrazines; cycloheptapyridazines; cycloheptapyrimidines; cycloheptaoxadiazines; cycloheptathiadiazines; cycloheptadiazaphosphorins cycloheptaquinoxalines; cycloheptatriazines; cycloheptathiatriazines; and cycloheptaoxatriazines.

N Valence Stabilizer #5a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates or N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacyclopentapyridines; tetraazacyclopentapyridines; diazacyclopentaquinolines; tetraazacyclopentaquinolines; diazacyclopentapyrazines; tetraazacyclopentapyrazines; diazacyclopentapyridazines; tetraazacyclopentapyridazines; diazacyclopentapyrimidines; tetraazacyclopentapyrimidines; diazacyclopentatriazines; and tetraazacyclopentatriazines.

N Valence Stabilizer #5b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacycloheptapyridines; tetraazacycloheptapyridines; diazacycloheptaquinolines; tetraazacycloheptaquinolines; diazacycloheptapyrazines; tetraazacycloheptapyrazines; diazacycloheptapyridazines; tetraazacycloheptapyridazines; diazacycloheptapyrimidines; tetraazacycloheptapyrimidines; diazacycloheptatriazines; and tetraazacycloheptatriazines.

N Valence Stabilizer #5c: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diazacyclononapyridines; tetraazacyclononapyridines; diazacyclononaquinolines; tetraazacyclononaquinolines; diazacyclononapyrazines; tetraazacyclononapyrazines; diazacyclononapyridazines; tetraazacyclononapyridazines; diazacyclononapyrimidines; tetraazacyclononapyrimidines; diazacyclononatriazines; and tetraazacyclononatriazines.

N Valence Stabilizer #6: Examples of silylamines and silazanes (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trisilylamine; N-methyldisilazane (disilylmethylamine); N,N-dimethylsilylamine; (silyldimethylamine); tris(trimethylsilyl)amine; triethylsilylamine (triethylaminosilane) (triethylsilazane); N-ethyltriethylsilylamine (triethyl-N-ethylaminosilane); di-tert-butylsilanediamine (di-tert-butyldiaminosilane); bis(methylamino)diethylsilane; tris(dimethylamino)ethylsilane; hexamethyldisilazane; N-methylhexaphenyldisilazane; hexamethylcyclotrisilazane; and octaphenylcyclotetrasilazane. [Note: Silylamines and silazanes are notably weaker ligands than their carbonaceous derivatives, although replacement of one or two SiR₃groups with CR₃will enhance the donor power of the ligand. Thus, N(CR₃)₂(SiR₃) is a better ligand than N(CR₃)(SiR₃)₂, etc.]

N Valence Stabilizer #7: Examples of guanidines, diguanidines, and polyguanidines (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: guanidine; methylguanidine; ethylguanidine; isopropylguanidine; butylguanidine; benzylguanidine; phenylguanidine; tolylguanidine; naphthylguanidine; cyclohexylguanidine; norbornylguanidine; adamantylguanidine; dimethylguanidine; diethylguanidine; diisopropylguanidine; dibutylguanidine; dibenzylguanidine; diphenylguanidine; ditolylguanidine; dinaphthylguanidine; dicyclohexylguanidine; dinorbornylguanidine; diadamantylguanidine; ethylenediguanidine; propylenediguanidine; tetramethylenediguanidine; pentamethylenediguanidine; hexamethylenediguanidine; heptamethylenediguanidine; octamethylenediguanidine; phenylenediguanidine; piperazinediguanidine; oxalyldiguanidine; malonyldiguanidine; succinyldiguanidine; glutaryldiguanidine; adipyldiguanidine; pimelyldiguanidine; suberyldiguanidine; phthalyldiguanidine; benzimidazoleguanidine; aminoguanidine; nitroaminoguanidine; dicyandiamide (cyanoguanidine); dodecylguanidine; and nitrovin.

N Valence Stabilizer #8: Examples of phosphonitrile amides and bis(phosphonitrile amides) (N—N Bidentates and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphononitrile amide; N-phenylphosphonitrile amide; N-benzylphosphonitrile amide; N-cyclohexylphosphonitrile amide; N-norbornylphosphonitrile amide; N,N′-diphenylphosphonitrile amide; N,N′-dibenzylphosphonitrile amide; N,N′-dicyclohexylphosphonitrile amide; and N,N′-dinorbornylphosphonitrile amide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N Valence Stabilizer #9: Examples of phosphonimidic diamides, bis(phosphonimidic diamides), and poly(phosphonimidic diamides) (N—N bidentates and N—N tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphonimidic diamide; N-benzylphosphonimidic diamide; N-phenylphosphonimidic diamide; N-cyclohexylphosphonimidic diamide; N-norbornylphosphonimidic diamide; N,N-dibenzylphosphonimidic diamide; N,N-diphenylphosphonimidic diamide; N,N-dicyclohexylphosphonimidic diamide; and N,N-dinorbornylphosphonimidic diamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N Valence Stabilizer #10: Examples of phosphonamidimidic acid, phosphonamidimidothioic acid, bis(phosphonamidimidic acid), bis(phosphonamidimidothioic acid), poly(phosphonamidimidic acid), poly(phosphonamidimidothioic acid), and derivatives thereof (N—N Bidentates, and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphonamidimidic acid, phosphonamidimidothioic acid; O-phenylphosphonamidimidic acid; O-benzylphosphonamidimidic acid; O-cyclohexylphosphonamidimidic acid; O-orbornylphosphonamidimidic acid; S-phenylphosphonamidimidothioic acid; S-enzylphosphonamidimidothioic acid; S-cyclohexylphosphonamidimidothioic acid; and S-orbornylphosphonamidimidothioic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

Valence Stabilizer #11: Examples of pyridinaldimines, bis(pyridinaldimines), and poly(pyridinaldimines) (N—N Bidentates, N—N Tridentates, and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pyridylideneaniline [N-(pyridylmethylene)benzenamine]; and (2-pyridyl)benzylideneaniline.

N Valence Stabilizer #12: Examples of hydrazones, bis(hydrazones), and poly(hydrazones) (N Monodentates, N—N Bidentates, N—N Tridentates, and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetaldehyde hydrazone; acetaldehyde phenylhydrazone; acetone hydrazone; acetone phenylhydrazone; pinacolone hydrazone; pinacolone phenylhydrazone; benzaldehyde hydrazone; benzaldehyde phenylhydrazone; naphthaldehyde hydrazone; naphthaldehyde phenylhydrazone; norbornanone hydrazone; norbornanone phenylhydrazone; camphor hydrazone; camphor phenylhydrazone; nopinone hydrazone; nopinone phenylhydrazine; 2-pyridinaldehyde hydrazone; 2-pyridinealdehyde phenylhydrazone; salicylaldehyde hydrazone; salicylaldehyde phenylhydrazone; quinolinaldehyde hydrazone; quinolinaldehyde phenylhydrazone; isatin dihydrazone; isatin di(phenylhydrazone); camphorquinone dihydrazone; camphorquinone di(phenylhydrazone); and 2-hydrazinobenzimidazole hydrazone.

N Valence Stabilizer #13: Examples of azo compounds without chelate substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, bis(azo compounds), or poly(azo compounds) (N Monodentates, N—N Bidentates, or N—N Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azobenzene (diphenyldiazene); p-diaminoazobenzene; p-dimethylaminoazobenzene (butter yellow); methyl orange; Fast Garnet GBC (4′-amino-2,3′-dimethylazobenzene)[Note: non-bonding methyl group in the o-position.]; and Alizarin Yellow R. [Note: Azo compounds without chelate substitution at the ortho- (for aryl) or beta- (for alkyl) positions tend to stabilize lower oxidation states in metal ions.]

N Valence Stabilizer #14: Examples of formazans, bis(formazans), and poly(formazans) without ortho- hydroxy, carboxy, thiol, mercapto, amino, or hydrazido substitution (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,3,5-triphenylformazan; and 1,3,5-naphthylformazan.

N Valence Stabilizer #15: Examples of hydramides (N—N Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hydrobenzamide; hydronaphthamide; and hydrosalicylamide.

N Valence Stabilizer #16: Examples of azines (including ketazines), bis(azines), and poly(azines) without ortho-hydroxy, carboxy, thiol, mercapto, amino, or hydrazido substitution (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: benzalazine; napbthalazine; cyclohexanonazine; and norbornonazine.

N Valence Stabilizer #17: Examples of Schiff Bases with one Imine (C═N) Group and without ortho- (for aryl constituents) or alpha- or beta- (for alkyl constituents) hydroxy, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido substitution (N Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-(Benzaldehydo)isopropylamine; N-(Naphthaldehydo)isopropylamine; N-(Acetophenono)isopropyl amine; N-(Propiophenono)isopropylamine; N-(Benzaldehydo)cyclohexylamine; N-(Naphthaldehydo)cyclohexylamine; N-(Acetophenono)cyclohexylamine; N-(Propiophenono)cyclohexylamine; N-(Benzaldehydo)aniline (BAAN); N-(Naphthaldehydo)aniline; N-(Acetophenono)aniline; N-(Propiophenono)aniline; N-(Benzaldehydo)aminonorbornane; N-(Naphthaldehydo)aminonorbornane; N-(Acetophenono)aminonorbornane; N-(Propiophenono)aminonorbornane; (Vanillino)anisidine; (Cinnamaldehydo)anisidine; N-(o-carboxycinnamaldehydo)aniline; N-(cinnamaldehydo)aniline; N-(cinnamaldehydo)m- or p-anisidine; and N-(o-carboxycinnamaldehydo)m- or p-anisidine.

N Valence Stabilizer #18: Examples of isocyanide and cyanamide and related ligands (N Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: isocyanate (—NCO); isothiocyanate (—NCS); isoselenocyanate (—NCSe); and cyanamide (—NCN). [Note: the nitrogen atom is directly complexed to the high valence metal ion.]

N Valence Stabilizer #19: Examples of nitrosyls and nitrites and related ligands (N Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: nitrosyl (—NO); thionitrosyl (—NS); nitrite (—NO₂); thionitrite (sulfinylamide)(thiazate)(—NSO); nitrosamine (═NN═O); thionitrosamine (NN═S); nitramine (═NNO₂); and thionitramine (═NNS₂) ligands.

N Valence Stabilizer #20: Examples of nitriles, dinitriles, and polynitriles (N Monodentates, N—N Bidentates, N—N Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: benzonitrile; naphthonitrile; cyanonaphthalene; cyclohexyl nitrile; cyanopyridine; cyanopurine; cyanophenol; cyanothiophenol; adamantane nitrile; norbornyl nitrile; cinnamonitrile; dicyanobenzene; dicyanobutene; dicyanoimidazole; dicyanopyridine; cyanotolunitrile; tetracyanoethylene (TCNE); tetracyanoquinodimethane (TCNQ); diethylaminopropionitrile (deapn), and polyacrylonitriles.

N Valence Stabilizer #21: Examples of azide ligands (N monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azide (—N₃) ions; methyl azide; ethyl azide; phenyl azide; diphenyltriazene; and phenyl sulfonyl azide.

S Valence Stabilizer #1: Examples of monothioethers (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hydrogen sulfide, dimethyl sulfide, diethyl sulfide, dioctyl sulfide, diphenyl sulfide, dicyclohexyl sulfide, tetramethylene sulfide (tetrahydrothiophene, tht), trimethylene sulfide, dimethylene sulfide (ethylene sulfide), pentamethylene sulfide, 1,4-thioxane, oxathiolane, cyclohexene sulfide, cyclooctene sulfide, benzotetrahydrothiophene, dibenzothiophene, naphthotetrahydrothiophene, and thiabicycloheptane.

S Valence Stabilizer #2: Examples of disulfides (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methyl disulfide, ethyl disulfide, phenyl disulfide, nitrophenide, and 1,2-dithiacyclohexane.

S Valence Stabilizer #3: Examples of dithioethers (S monodentates or S—S bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,3-dithiane, 1,4-dithiane, benzodithiane, dibenzodithiane, naphthodithiane, 2,5-dithiahexane (dth); 3,6-dithiaoctane (dto); 2,5-dimethyl-3,6-dithiaoctane; 3,7-dithianonane; 2,6-dithiaheptane; 1,6-diphenyl-2,5-dithiahexane; 1,4-dipbenyl-1,4-dithiabutane; 1,3-dithiolane; 1,4-dithiane (1,4-dithiacyclohexane); 1,4-dithiacycloheptane (dtch); 1,5-dithiacyclooctane (dtco); o-phenylenebis(2-thiapropane); o-phenylenebis(2-thiabutane); 2,2′-(thiamethyl)biphenyl, and 2,2′-(thiaethyl)biphenyl.

S Valence Stabilizer #4: Examples of trithioethers (S monodentates, S—S bidentates, or S—S tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,3,5-trithiane; 1,3,5-tris(methylthia)cyclohexane; 1,3,5-tris(ethylthia)cyclohexane; 1,3,5-tris(phenylthia)cyclohexane; 2,5,8-trithianonane; 3,6,9-trithiaundecane; and 2,6,10-trithiaundecane.

S Valence Stabilizer #5: Examples of tetrathioetbers (S monodentates, S—S bidentates, S—S tridentates, or S—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,4,10,13-tetrathiatridecane; 2,6,10,14-tetrathiapentadecane; 2,5,8,11-tetrathiadodecane; 2,5,9,12-ttetrathiatridecane; 2,6,9,13-tetrathiatetradecane; 1,4-(o-thiomethyl)phenyl-1,4-dithiabutane; 1,5-(o-thiomethyl)phenyl-1,5-dithiapentane; 1,6-(o-thiomethyl)phenyl-1,6-dithiahexane; 1,4-(o-thiomethyl)phenyl-1,4-dithiabut-2-ene; and polythioethers.

S Valence Stabilizer #6: Examples of hexathioethers (S monodentates, S—S bidentates, S—S tridentates, S—S tetradentates, or S—S hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tri(2-((o-thiomethyl)phenyl)ethyl)amine; and tri((o-thiomethyl)phenyl)methylamine.

S Valence Stabilizer #7a: Examples of 5-membered heterocyclic rings containing one sulfur atom (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydrothiophene, thiophene, thiazole, thiapyrroline, thiaphospholene, thiaphosphole, oxathiole, thiadiazole, thiatriazole, benzodihydrothiophene, benzothiophene, benzothiazole, benzothiaphosphole, dibenzothiophene, and naphthothiophene.

S Valence Stabilizer #7b: Examples of 5-membered heterocyclic rings containing two sulfur atoms (S monodentates or S—S bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiole, benzodithiole, and naphthodithiole.

S Valence Stabilizer #8a: Examples of 6-membered heterocyclic rings containing one sulfur atom (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydrothiopyran, thiopyran, thiazine, thiadiazine, thiaphosphorin, thiadiphosphorin, oxathiin, benzothiopyran, dibenzothiopyran, and naphthothiopyran.

S Valence Stabilizer #8b: Examples of 6-membered heterocyclic rings containing two sulfur atoms (S monodentates or S—S bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydrodithiin, dithiin, benzodithiin, dibenzodithiin (thianthrene), and naphthodithiin.

S Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,5-dimercapto-2,5-dihydrothiophene; 2,5-bis(thiomethyl)-2,5-dihydrothiophene; 2,5-bis(2-thiophenyl)-2,5-dihydrothiophene; 2,5-dimercaptothiophene; 2,5-bis(thiomethyl)thiophene; 2,5-bis(2-thiophenyl)thiophene; 2,5-dimercatothiazole; 2,5-bis(thiomethyl)thiazole; 2,5-bis(2-thiophenyl)thiazole; 2,5-dimercapto-1,3,4-thiadiazole [bismuththiol]; 2-mercaptothianaphthene; 7-(thiomethyl)thianaphthene; 1,8-dimercaptodibenzothiophene; 2-mercaptobenzothiazole; 2-mercapro-1,3,4-thiadiazole; 2-amino-5-mercapto-1,3,4-thiadiazole; 2,5-bis(alkylthio)-1,3,4-thiadiazole; and 7-(thiomethyl)benzothiazole.

S Valence Stabilizer #9b: Examples of 5-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-mercapto-1,3-dithiole; 2-(dimercaptomethyl)-1,3-dithiole; 4,5-dimercapto-1,3-dithiole; 4,5-bis(2-thiophenyl)-1,3-dithiole; 2-mercaptobenzodithiole; and 7-mercaptobenzodithiole.

S Valence Stabilizer #10a: Examples of 6-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,6-dimercapto-2,5-dihydrothiopyran; 2,6-bis(thiomethyl)-2,5-dihydrothiopyran; 2,6-bis(2-thiophenyl)-2,5-dihydrothiopyran; 2,6-dimercaptothiopyran; 2,6-bis(thiomethyl)thiopyran; 2,6-bis(2-thiophenyl)thiopyran; 2,6-dimercaptothiazine; 2,6-bis(thiomethyl)thiazine; 2,6-bis(2-thiophenyl)thiazine; 2,6-dimercapto-1,3,5-thiadiazine; 2-mercapto-1-benzothiopyran; 8-mercapto-1-benzothiopyran; and 1,9-dimercaptodibenzothiopyran.

S Valence Stabilizer #10b: Examples of 6-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-mercapto-1,4-dithiin; 2,6-dimercapto-1,4-dithiin; 2,6-bis(2-thiophenyl)-1,4-dithiin; 2,3-dimercapto-1,4-benzodithiin; 5,8-dimercapto-1,4-benzodithiin; 1,8-dimercaptothianthrene; and 1,4,5,8-tetramercaptothianthrene.

S Valence Stabilizer #11a: Examples of 5-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-2,5-dihydrothiophene; 2,2′,2″-tri-2,5-dihydrothiophene; 2,2′-bithiophene; 2,2′,2″-trithiophene; 2,2′-bithiazole; 5,5′-bithiazole; 2,2′-bioxathiole; 2,2′-bi-1,3,4-thiadiazole; 2,2′-bithianaphthene; 2,2′-bibenzothiazole; 1,1′-bis(dibenzothiophene); and polythiophenes.

S Valence Stabilizer #11b: Examples of 5-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,3-dithiole; 4,4′-bi-1,3-dithiole; 7,7′-bi-1,2-benzodithiole; 3,3′-bi-1,2-benzodithiole; and tetrathiofulvalene.

S Valence Stabilizer #12a: Examples of 6-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-2,5-dihydrothiopyran; 2,2′,2″-tri-2,5-dihydrothiopyran; 2,2′-bithiopyran; 2,2′,2″-trithiopyran; 2,2′-bi-1,4-thiazine; 2,2′-bi-1,3,5-thiadiazine; 2,2′-bi-1-benzothiopyran; and 1,1′-bis(dibenzothiopyran)

S Valence Stabilizer #12b: Examples of 6-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,4-dithiin; 2,2′-bi-1,3-dithiin; 5,5′-bi-1,4-benzodithiin; 2,2′-bi-1,3-benzodithiin; and 1,1′-bithianthrene.

S Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiacyclobutane ([4]aneS₂); dithiacyclopentane ([5]aneS₂); dithiacyclohexane ([6]aneS₂); dithiacycloheptane ([7]aneS₂); dithiacyclooctane ([8]aneS₂); dithiacyclobutene ([4]cneS₂); dithiacyclopentene ([5]eneS₂); dithiacyclohexene ([6]eneS₂); dithiacycloheptene ([7]eneS₂); dithiacyclooctene ([8]eneS₂); dithiacyclobutadiene ([4]dieneS₂); dithiacyclopentadiene ([5]dieneS₂); dithiacyclohexadiene ([6]dieneS₂); dithiacycloheptadiene ([7]dieneS₂); and dithiacyclooctadiene ([8]dieneS₂).

S Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithiacyclohexane ([6]aneS₃); trithiacycloheptane ([7]aneS₃); trithiacyclooctane ([8]aneS₃); trithiacyclononane ([9]aneS₃); trithiacyclodecane ([10]aneS₃); trithiacycloundecane ([11]aneS₃); trithiacyclododecane ([12]aneS₃); trithiacyclohexene ([6]eneS₃); trithiacycloheptene ([7]eneS₃); trithiacyclooctene ([8]eneS₃); trithiacyclononene ([9]eneS₃); trithiacyclodecene ([10]eneS₃); trithiacycloundecene ([11]eneS₃); trithiacyclododecene ([12]eneS₃); trithiacyclohexatriene ([6]trieneS₃); trithiacycloheptatriene ([7]trieneS₃); trithiacyclooctatriene ([8]trieneS₃); trithiacyclononatriene ([9]trieneS₃); trithiacyclodecatriene ([10]trieneS₃); trithiacycloundecatriene ([11]trieneS₃); and trithiacyclododecatriene ([12]trieneS₃).

S Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrathiacyclooctane ([8]aneS₄); tetrathiacyclononane ([9]aneS₄); tetrathiacyclodecane ([10]aneS₄); tetrathiacycloundecane ([11]aneS₄); tetrathiacyclododecane ([12]aneS₄); tetrathiacyclotridecane ([13]aneS₄); tetrathiacyclotetradecane ([14]aneS₄); tetrathiacyclopentadecane ([15]aneS₄); tetrathiacyclohexadecane ([16]aneS₄); tetrathiacycloheptadecane ([17]aneS₄); tetrathiacyclooctadecane ([18]aneS₄); tetrathiacyclononadecane ([19]aneS₄); tetrathiacycloeicosane ([20]aneS₄); tetrathiacyclooctadiene ([8]dieneS₄); tetrathiacyclononadiene ([9]dieneS₄); tetrathiacyclodecadiene ([10]dieneS₄); tetrathiacycloundecadiene ([11]dieneS₄); tetrathiacyclododecadiene ([12]dieneS₄); tetrathiacyclotridecadiene ([13]dieneS₄); tetrathiacyclotetradecadiene ([14]dieneS₄); tetrathiacyclopentadecadiene ([15]dieneS₄); tetrathiacyclohexadecadiene ([16]dieneS₄); tetrathiacycloheptadecadiene ([17]dieneS₄); tetrathiacyclooctadecadiene ([18]dieneS₄); tetrathiacyclononadecadiene ([19]dieneS₄); tetrathiacycloeicosadiene ([20]dieneS₄); tetrathiacyclooctatetradiene ([8]tetradieneS₄); tetrathiacyclononatetradiene ([9]tetradieneS₄); tetrathiacyclodecatetradiene ([10]tetradieneS₄); tetrathiacycloundecatetradiene ([11]tetradieneS₄); tetrathiacyclododecatetradiene ([12]tetradieneS₄); tetrathiacyclotridecatetradiene ([13]tetradieneS₄); tetrathiacyclotetradecatetradiene ([14]tetradieneS₄); tetrathiacyclopentadecatetradiene ([15]tetradieneS₄); tetrathiacyclohexadecatetradiene ([16]tetradieneS₄); tetrathiacycloheptadecatetradiene ([17]tetradieneS₄); tetrathiacyclooctadecatetradiene ([18]tetradieneS₄); tetrathiacyclononadecatetradiene ([19]tetradieneS₄); and tetrathiacycloeicosatetradiene ([20]tetradieneS₄).

S Valence Stabilizer #13d: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pentathiacyclodecane ([10]aneS₅); pentathiacycloundecane ([11]aneS₅); pentathiacyclododecane ([12]aneS₅); pentathiacyclotridecane ([13]aneS₅); pentathiacyclotetradecane ([14]aneS₅); pentathiacyclopentadecane ([15]aneS₅); pentathiacyclodecatriene ([10]trieneS₅); pentathiacycloundecatriene ([11]trieneS₅); pentathiacyclododecatriene ([12]trieneS₅); pentathiacyclotridecatriene ([13]trieneS₅); pentathiacyclotetradecatriene ([14]trieneS₅); and pentathiacyclopentadecatriene ([15]trieneS₅).

S Valence Stabilizer #13e: Examples of six-membered macrocyclics,-macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexathiacyclododecane ([12]aneS₆); hexathiacyclotridecane ([13]aneS₆); hexathiacyclotetradecane ([14]aneS₆); hexathiacyclopentadecane ([15]aneS₆); hexathiacyclohexadecane ([16]aneS₆); hexathiacycloheptadecane ([17]aneS₆); hexathiacyclooctadecane ([18]aneS₆); hexathiacyclononadecane ([19]aneS₆); hexathiacycloeicosane ([20]aneS₆); hexathiacycloheneicosane ([21]aneS₆); hexathiacyclodocosane ([22]aneS₆); hexathiacyclotricosane ([23]aneS₆); hexathiacyclotetracosane ([24]aneS₆); hexathiacyclododecatriene ([12]trieneS₆); hexathiacyclotridecatriene ([13]trieneS₆); hexathiacyclotetradecatriene ([14]trieneS₆); hexathiacyclopentadecatriene ([15]trieneS₆); hexathiacyclohexadecatriene ([16]trieneS₆); hexathiacycloheptadecatriene ([17]trieneS₆); hexathiacyclooctadecatriene ([18]trieneS₆); hexathiacyclononadecatriene ([19]trieneS₆); hexathiacycloeicosatriene ([20]trieneS₆); hexathiacycloheneicosatriene ([21]trieneS₆); hexathiacyclodocosatriene ([22]trieneS₆); hexathiacyclotricosatriene ([23]trieneS₆); and hexathiacyclotetracosatriene ([24]trieneS₆).

S Valence Stabilizer #13f: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: heptathiacyclotetradecane ([14]aneS₇); heptathiacyclopentadecane ([15]aneS₇); heptathiacyclohexadecane ([16]aneS₇); heptathiacycloheptadecane ([17]aneS₇); heptathiacyclooctadecane ([18]aneS₇); heptathiacyclononadecane ([19]aneS₇); heptathiacycloeicosane ([20]aneS₇); heptathiacycloheneicosane ([21]aneS₇); heptathiacyclotetradecatriene ([14]trieneS₇); heptathiacyclopentadecatriene ([15]trieneS₇); heptathiacyclohexadecatriene ([16]trieneS₇); heptathiacycloheptadecatriene ([17]trieneS₇); heptathiacyclooctadecatriene ([18]trieneS₇); heptathiacyclononadecatri ene ([19]trieneS₇); heptathiacycloeicosatriene ([20]trieneS₇); and heptathiacycloheneicosatriene ([21]trieneS₇).

S Valence Stabilizer #13g: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: octathiacyclohexadecane ([16]aneS₈); octathiacycloheptadecane ([17]aneS₈); octathiacyclooctadecane ([18]aneS₈); octathiacyclononadecane ([19]aneS₈); octathiacycloeicosane ([20]aneS₈); octathiacycloheneicosane ([21]aneS₈); octathiacyclodocosane ([22]aneS₈); octathiacyclotricosane ([23]aneS8); octathiacyclotetracosane ([24]aneS₈); octathiacyclohexadecatetradiene ([16]tetradieneS₈); octathiacycloheptadecatetradiene ([17]tetradieneS₈); octathiacyclooctadecatetradiene ([18]tetradieneS₈); octathiacyclononadecatetradiene ([19]tetradieneS₈); octathiacycloeicosatetradiene ([20]tetradieneS₈); octathiacycloheneicosatetradiene ([21]tetradieneS₈); octathiacyclodocosatetradiene ([22]tetradieneS₈); octathiacyclotricosatetradiene ([23]tetradieneS₈); and octathiacyclotetracosatetradiene ([24]tetradieneS₈).

S Valence Stabilizer #13h: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: nonathiacyclooctadecane ([18]aneS₉); nonathiacyclononadecane ([19]aneS₉); nonathiacycloeicosane ([20]aneS₉); nonathiacycloheneicosane ([21]aneS₉); nonathiacyclodocosane ([22]aneS₉); nonathiacyclotricosane ([23]aneS₉); nonathiacyclotetracosane ([24]aneS₉); nonathiacyclopentacosane ([25]aneS₉); nonathiacyclohexacosane ([26]aneS₉); nonathiacycloheptacosane ([27]aneS₉); nonathiacyclooctadecatetradiene ([18]tetradieneS₉); nonathiacyclononadecatetradiene ([19]tetradieneS₉); nonathiacycloeicosatetradiene ([20]tetradieneS₉); nonathiacycloheneicosatetradiene ([21]tetradieneS₉); nonathiacyclodocosatetradiene ([22]tetradieneS₉); nonathiacyclotricosatetradiene ([23]tetradieneS₉); nonathiacyclotetracosatetradiene ([24]tetradieneS₉); nonathiacyclopentacosatetradiene ([25]tetradieneS₉); nonathiacyclohexacosatetradiene ([26]tetradieneS₉); and nonathiacycloheptacosatetradiene ([27]tetradieneS₉).

S Valence Stabilizer #13i: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: decathiacycloeicosane ([20]aneS₁₀); decathiacycloheneicosane ([21]aneS₁₀); decathiacyclodocosane ([22]aneS₁₀); decathiacyclotricosane ([23]aneS₁₀); decathiacyclotetracosane ([24]aneS₁₀); decathiacyclopentacosane ([25]aneS₁₀); decathiacyclohexacosane ([26]aneS₁₀); decathiacycloheptacosane ([27]aneS₁₀); decathiacyclooctacosane ([28]aneS₁₀); decathiacyclononacosane ([29]aneS₁₀); decathiacyclotriacontane ([30]aneS₁₀); decathiacycloeicosapentadiene ([20]pentadieneS₁₀); decathiacycloheneicosapentadiene ([21]pentadieneS₁₀); decathiacyclodocosapentadiene ([22]pentadieneS₁₀); decathiacyclotricosapentadiene ([23]pentadieneS₁₀); decathiacyclotetracosapentadiene ([24]pentadieneS₁₀); decathiacyclopentacosapentadiene ([25]pentadieneS₁₀); decathiacyclohexacosapentadiene ([26]pentadieneS₁₀); decathiacycloheptacosapentadiene ([27]pentadieneS₁₀); decathiacyclooctacosapentadiene ([28]pentadieneS₁₀); decathiacyclononacosapentadiene ([29]pentadieneS₁₀); and decathiacyclotriacontapentadiene ([30]pentadieneS₁₀).

S Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrathiophenes; tetrathiazoles; tetrathiaphospholes; tetraoxathioles; tetrathiadiazoles; tetrathiatriazoles; and tetradithioles.

S Valence Stabilizer #14b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pentathiophenes; pentathiazoles; pentathiaphospholes; pentaoxathioles; pentathiadiazoles; pentathiatriazoles; and pentadithioles.

S Valence Stabilizer #14c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexathiophenes; hexathiazoles; hexathiaphospholes; hexaoxathioles; hexathiadiazoles; hexathiatriazol es; and hexadithioles.

S Valence Stabilizer #14d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: heptathiophenes; heptathiazoles; heptathiaphospholes; heptaoxathioles; heptathiadiazoles; heptathiatriazoles; and heptadithioles.

S Valence Stabilizer #14e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: octathiophenes; octathiazoles; octathiaphospholes; octaoxathioles; octathiadiazoles; octathiatriazoles; and octadithioles.

S Valence Stabilizer #14f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: nonathiophenes; nonathiazoles; nonathiaphospholes; nonaoxathioles; nonathiadiazoles; nonathiatriazoles; and nonadithioles.

S Valence Stabilizer #14g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn include, but are not limited to: decathiophenes; decathiazoles; decathiaphospholes; decaoxathioles; decathiadiazoles; decathiatriazoles; and decadithioles.

S Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiatetrathiophenes; tetrathiatetrathiophenes; dithiatetradithioles; and tetrathiatetradithioles.

S Valence Stabilizer #15b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiapentathiophenes; tetrathiapentathiophenes; dithiapentadithioles; and tetrathiapentadithioles.

S Valence Stabilizer #15c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiahexaathiophenes; trithiahexathiophenes; dithiahexadithioles; and trithiahexadithioles.

S Valence Stabilizer #15d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiaheptathiophenes; tetrathiaheptathiophenes; dithiaheptadithioles; and tetrathiaheptadithioles.

S Valence Stabilizer #15e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiaoctathiophenes; tetrathiaoctathiophenes; dithiaoctadithioles; and tetrathiaoctadithioles.

S Valence Stabilizer #15f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithianonathiophenes; hexathianonathiophenes; trithianonadithioles; and hexathianonadithioles.

S Valence Stabilizer #15g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiadecathiophenes; pentathiadecathiophenes; dithiadecadithioles; and pentathiadecadithioles.

S Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrathiopyrans; tetrathiazines; tetrathiaphosphorins; tetrathiadiphosphorins; tetraoxathiins; and tetradithiins.

S Valence Stabilizer #16b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pentathiopyrans; pentathiazines; pentathiaphosphorins; pentathiadiphosphorins; pentaoxathiins; and pentadithins.

S Valence Stabilizer #16c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexathiopyrans; hexathiazines; hexathiaphosphorins; hexathiadiphosphorins; hexaoxathiins; and hexadithiins.

S Valence Stabilizer #16d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: heptathiopyrans; heptathiazines; heptathiaphosphorins; heptathiadiphosphorins; heptaoxathiins; and heptadithiins.

S Valence Stabilizer #16e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: octathiopyrans; octathiazines; octathiaphosphorins; octathiadiphosphorins; octaoxathiins; and octadithiins.

S Valence Stabilizer #16f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: nonathiopyrans; nonathiazines; nonathiaphosphorins; nonathiadiphosphorins; nonaoxathiins; and nonadithiins.

S Valence Stabilizer #16g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: decathiopyrans; decathiazines; decatbiaphosphorins; decathiadiphosphorins; decaoxathiins; and decadithiins.

S Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiatetrathiopyrans; tetrathiatetrathiopyrans; dithiatetrathiazines; tetrathiatetrathiazines; dithiatetrathiaphosphorins; tetrathiatetrathiaphosphorins; dithiatetraoxathiins; tetrathiatetraoxathiins; dithiatetradithiins; and tetrathiatetradithiins.

S Valence Stabilizer #17b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiapentathiopyrans; tetrathiapentathiopyrans; dithiapentathiazines; tetrathiapentathiazines; dithiapentathiaphosphorins; tetrathiapentathiaphosphorins; dithiapentaoxathiins; tetrathiapentaoxathiins; dithiapentadithiins; and tetrathiapentadithiins.

S Valence Stabilizer #17c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiahexathiopyrans; trithiahexathiopyrans; dithiahexathiazines; trithiahexathiazines; dithiahexathiaphosphorins; trithiahexathiaphosphorins; dithiahexaoxathiins; trithiahexaoxathiins; dithiahexadithiins; and trithiahexadithiins.

S Valence Stabilizer #17d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiaheptathiopyrans; tetrathiaheptathiopyrans; dithiaheptathiazines; tetrathiaheptathiazines; dithiaheptathiaphosphorins; tetrathiaheptathiaphosphorins; dithiaheptaoxathiins; tetrathiaheptaoxathiins; dithiaheptadithiins; and tetrathiaheptadithiins.

S Valence Stabilizer #17e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiaoctathiopyrans; tetrathiaoctathiopyrans; dithiaoctathiazines; tetrathiaoctathiazines; dithiaoctathiaphosphorins; tetrathiaoctathiaphosphorins; dithiaoctaoxathiins; tetrathiaoctaoxathiins; dithiaoctadithiins; and tetrathiaoctadithiins.

S Valence Stabilizer #17f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithianonathiopyrans; hexathianonathiopyrans; trithianonathiazines; hexathianonathiazines; trithianonathiaphosphorins; hexathianonathiaphosphorins; trithianonaoxathiins; hexathianonaoxathiins; trithianonadithiins; and hexathianonadithiins.

S Valence Stabilizer #17g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiadecathiopyrans; pentathiadecathiopyrans; dithiadecathiazines; pentathiadecathiazines; dithiadecathiaphosphorins; pentathiadecathiaphosphorins; dithiadecaoxathiins; pentathiadecaoxathiins; dithiadecadithins; and pentathiadecadithiins.

S Valence Stabilizer #18: Examples of dithiobiurets (dithioimidodicarbonic diamides), dithioisobiurets, dithiobiureas, trithiotriurets, trithiotriureas, bis(dithiobiurets), bis(dithioisobiurets), bis(dithiobiureas), poly(dithiobiurets), poly(dithioisobiurets), and poly(dithiobiureas) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiobiuret, dithioisobiuret, dithiobiurea, trithiotriuret, trithiotriurea, nitrodithiobiuret, dinitrodithiobiuret, aminodithiobiuret, diaminodithiobiuret, oxydithiobiuret, dioxydithiobiuret, cyanodithiobiuret, methyldithiobiuret, ethyldithiobiuret, isopropyldithiobiuret, phenyldithiobiuret, benzyldithiobiuret, cyclohexyldithiobiuret, norbornyldithiobiuret, adamantyldithiobiuret, dimethyldithiobiuret, diethyldithiobiuret, diisopropyldithiobiuret, diphenyldithiobiuret, dibenzyldithiobiuret, dicyclohexyldithiobiuret, dinorbornyldithiobiuret, and diadamantyldithiobiuret.

S Valence Stabilizer #19: Examples of thioacylthioureas, thioaroylthioureas, bis(thioacylthioureas), bis(thioaroylthioureas), poly(thioacylthioureas), and poly(thioaroylthioureas) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thioformylthiourea, thioacetylthiourea, thiobenzoylthiourea, thiocyclohexoylthiourea, pentafluorothiobenzoylthiourea, N-methylthioacetylthiourea, N-phenylthiobenzoylthiourea, and N-cyclohexylthiocyclohexoylthiourea.

S Valence Stabilizer #20: Examples of dithioacyl disulfides, bis(dithioacyl disulfides), and poly(dithioacyl disulfides), (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioacetyl disulfide; dithiopropanoyl disulfide; dithiobenzoyl disulfide; and dithiopentafluorobenzoyl disulfide.

S Valence Stabilizer #21: Examples of tetrathioperoxydicarbonic diamides, bis(tetrathioperoxydicarbonic diamides), and poly(tetrathioperoxydicarbonic diamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrathioperoxydicarbonic diamide; N-phenyltetrathioperoxydicarbonic diamide; N-benzyltetrathioperoxydicarbonic diamide; N-cyclohexyltetrathioperoxydicarbonic diamide; N-norbornyltetrathioperoxydicarbonic diamide; N,N′-diphenyltetrathioperoxydicarbonic diamide; N,N′-dibenzyltetrathioperoxydicarbonic diamide; N,N′-dicyclohexyltetrathioperoxydicarbonic diamide; and N,N′-dinorbornyltetrathioperoxydicarbonic diamide.

S Valence Stabilizer #22: Examples of hexathio-, pentathio-, and tetrathioperoxydicarbonic acids, bis(hexathio-, pentathio-, and tetrathioperoxydicarbonic acids), poly(hexathio-, pentathio-, and tetrathioperoxydicarbonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexathioperoxydicarbonic acid, pentathioperoxydicarbonic acid, tetrathioperoxydicarbonic acid, S-phenylhexathioperoxydicarbonic acid; S-benzylhexathioperoxydicarbonic acid; S-cyclohexylhexathioperoxydicarbonic acid; S-norbornylhexathioperoxydicarbonic acid; S,S′-diphenylhexathioperoxydicarbonic acid; S,S′dibenzylhexathioperoxydicarbonic acid; S,S′-dicyclohexylhexathioperoxydicarbonic acid; and S,S′-dinorbornylhexathioperoxydicarbonic acid.

S Valence Stabilizer #23: Examples of dithioperoxydiphosphoramides, bis(dithioperoxydiphosphoramides), and poly(dithioperoxydiphosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioperoxydiphosphoramide, N-methyldithioperoxydiphosphoramide, N-isopropyldithioperoxydiphosphoramide, N-tert-butyldithioperoxydiphosphoramide, N-phenyldithioperoxydiphosphoramide, N-pentafluorophenyldithioperoxydiphosphoramide, N-benzyldithioperoxydiphosphoramide, N-cyclohexyldithioperoxydiphosphoramide, N-norbornyldithioperoxydiphosphoramide, N,N′″-dimethyldithioperoxydiphosphoramide, N,N′″-diisopropyldithioperoxydiphosphoramide, N,N′″-di-tert-butyldithioperoxydiphosphoramide, N,N′″-diphenyldithioperoxydiphosphoramide, N,N′″-di-pentafluorophenyldithioperoxydiphosphoramide, N,N′″-dibenzyldithioperoxydiphosphoramide, N,N′″-dicyclohexyldithioperoxydiphosphoramide, and N,N′″-dinorbornyldithioperoxydiphosphoramide.

S Valence Stabilizer #24: Examples of dithioperoxydiphosphoric acids, bis(dithioperoxydiphosphoric acids), poly(dithioperoxydiphosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioperoxydiphosphoric acid, methyldithioperoxydiphospboric acid, isopropyldithioperoxydiphosphoric acid, tert-butyldithioperoxydiphosphoric acid, phenyldithioperoxydiphosphoric acid, pentafluorophenyldithioperoxydiphosphoric acid, benzyldithioperoxydiphosphoric acid, cyclohexyldithioperoxydiphosphoric acid, norbornyldithioperoxydiphosphoric acid, dimethyldithioperoxydiphosphoric acid, diisopropyldithioperoxydiphosphoric acid, di-tert-butyldithioperoxydiphosphoric acid, diphenyldithioperoxydiphosphoric acid, di-pentafluoropbenyldithioperoxydiphosphori c acid, dibenzyldithioperoxydiphosphoric acid, dicyclohexyldithioperoxydiphosphoric acid, and dinorbornyldithioperoxydiphosphoric acid.

S Valence Stabilizer #25: Examples of dithioimidodiphosphonic acids, dithiohydrazidodiphosphonic acids, bis(dithioimidodiphosphonic acids), bis(dithiohydrazidodipbosphonic acids), poly(dithioimidodiphosphonic acids), poly(dithiohydrazidodiphosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioimidodiphosphonic acid, methyldithioimidodiphosphonic acid, isopropyldithioimidodiphosphonic acid, tert-butyldithioimidodiphospbonic acid, phenyldithioimidodiphosphonic acid, pentafluorophenyldithioimidodiphosphonic acid, benzyldithioimidodiphosphonic acid, cyclohexyldithioimidodiphosphonic acid, norbornyldithioimidodiphosphonic acid, dimethyldithioimidodiphosphonic acid, diisopropyldiothioimidodiphosphonic acid, di-tert-butyldithioimidodiphosphonic acid, diphenyldithioimidodipbosphonic acid, di-pentafluorophenyldithioimidodiphosphonic acid, dibenzyldithioimidodiphosphonic acid, dicyclohexyldithioimidodiphosphonic acid, and dinorbornyldithioimidodiphosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #26: Examples of dithioimidodiphosphonamides, dithiohydrazidodiphosphonamides, bis(dithioimidodiphosphonamides), bis(dithiohydrazidodiphosphonamides), poly(dithioimidodiphosphonamides), and poly(dithiohydrazidodiphosphonamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioimidodiphosphonamide, N-methyldithioimidodiphosphonamide, N-isopropyl dithioimidodiphosphonamide, N-tert-butyldithioimidodiphosphonamide, N-phenyldithioimidodiphosphonamide, N-pentafluorophenyldithioimidodiphosphonamide, N-benzyldithioimidodiphosphonamide, N-cyclohexyldithioimidodiphosphonamide, N-norbornyldithioimidodiphosphonamide, N,N′″-dimethyldithioimidodiphosphonamide, N,N′″-diisopropyldithioimidodiphosphonamide, N,N′″-di-tert-butyldithioimidodiphosphonamide, N,N′″-diphenyldithioimidodiphosphonamide, N,N′″-di-pentafluorophenyldithioimidodiphosphonamide, N,N′″-dibenzyldithioimidodiphosphonamide, N,N′″-dicyclohexyldithioimidodiphosphonamide, and N,N′″-dinorbornyldithioimidodiphosphonamide. [Note: The phosphite (p+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #27: Examples of dithiodiphosphonamides, bis(dithiodiphosphonamides), and poly(dithiodiphosphonamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meetthe requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodiphosphonamide, N-methyldithiodiphosphonamide, N-isopropyldithiodiphosphonamide, N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide, N-pentafluorophenyldithiodiphosphonamide, N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide, N-norbornyldithiodiphosphonamide, N,N′″-dimethyldithiodiphosphonamide, N,N′″-diisopropyldithiodiphosphonamide, N,N′″-di-tert-butyldithiodiphosphonamidc, N,N′″-diphenyldithiodiphosphonamide, N,N′″-di-pentafluorophenyldithiodiphosphonamide, N,N′″-dibenzyldithiodiphosphonamide, N,N′″-dicyclohexyldithiodiphosphonamide, and N,N′″-dinorbornyldithiodiphosphonamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #28: Examples of dithiodiphosphonic acids, bis(dithiodiphosphonic acids), poly(dithiodiphosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodiphosphonic acid, methyldithiodiphosphonic acid, isopropyldithiodiphosphonic acid, tert-butyldithiodiphosphonic acid, phenyldithiodiphosphonic acid, pentafluorophenyldithiodiphosphonic acid, benzyldithiodiphosphonic acid, cyclohexyldithiodiphosphonic acid, norbornyldithiodiphosphonic acid, dimethyldithiodiphosphonic acid, diisopropyldiothiodiphosphonic acid, di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic acid, di-pentafluorophenyldithiodiphosphonic acid, dib,enzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphonic acid, and dinorbornyldithiodiphosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #29: Examples of dithioperoxydiphosphonamides, bis(dithioperoxydiphosphonamides), and poly(dithioperoxydiphosphonamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioperoxydiphosphonamide, N-methyldithioperoxydiphosphonamide, N-isopropyldithioperoxydiphosphonamide, N-tert-butyldithioperoxydiphosphonamide, N-phenyldithioperoxydiphosphonamide, N-pentafluorophenyldithioperoxydiphosphonamide, N-benzyldithioperoxydiphosphonamide, N-cyclohexyldithioperoxydiphosphonamide, N-norbornyldithioperoxydiphosphonamide, N,N′″-dimethyldithioperoxydiphosphonamide, N,N′″-diisopropyldithioperoxydiphosphonamide, N,N′″-di-tert-butyldithioperoxydiphosphonamide, N,N′″-diphenyldithioperoxydiphosphonamide, N,N′″-di-pentafluorophenyldithioperoxydiphosphonamide, N,N′″-dibenzyldithioperoxydiphosphonamide, N,N′″-dicyclohexyldithioperoxydiphosphonamide, and N,N′″-dinorbornyldithioperoxydiphosphonamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #30: Examples of dithioperoxydiphosphonic acids, bis(dithioperoxydiphosphonic acids), poly(dithioperoxydiphosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioperoxydiphosphonic acid, methyldithioperoxydiphosphonic acid, isopropyldithioperoxydiphosphonic acid, tert-butyldithioperoxydiphosphonic acid, phenyldithioperoxydiphosphonic acid, pentafluorophenyldithioperoxydiphosphonic acid, benzyldithioperoxydiphosphonic acid, cyclohexyldithioperoxydiphosphonic acid, norbornyldithioperoxydiphosphonic acid, dimethyldithioperoxydiphosphonic acid, diisopropyldithioperoxydiphosphonic acid, di-tert-butyldithioperoxydiphosphonic acid, diphenyldithioperoxydiphosphonic acid, di-pentafluorophenyldithioperoxydiphosphonic acid, dibenzyldithioperoxydiphosphonic acid, dicyclohexyldithioperoxydiphosphonic acid, and dinorbornyldithioperoxydiphosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #31: Examples of dithiophosphonic acids (phosphonodithioic acids), bis(dithiophosphonic acids), poly(dithiophosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiophosphonic acid, O-phenyldithiophosphonic acid, O-benzyldithiophosphonic acid, O-cyclohexyldithiophosphonic acid, O-norbornyldithiophosphonic acid, O,P-diphenyldithiophosphonic acid, O,P-dibenzyldithiophosphonic acid, O,P-dicyclohexyldithiophosphonic acid, and O,P-dinorbornyldithiophosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #32: Examples of trithiophosphonic acids (phosphonotrithioic acids), bis(trithiophosphonic acids), poly(trithiophosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithiophosphonic acid, S-phenyltrithiophosphonic acid, S-benzyltrithiophosphonic acid, S-cyclohexyltrithiophosphonic acid, S-norbornyltrithiophosphonic acid, S,P-diphenyltrithiophosphonic acid, S,P-dibenzyltrithiophosphonic acid, S,P-dicyclohexyltrithiophosphonic acid, and S,P-dinorbornyltrithiophosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.] S Valence Stabilizer #33: Examples of phosphono(dithioperoxo)thioic acids, bis[phosphono(dithioperoxo)thioic acids], poly[phosphono(dithioperoxo)thioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn⁺³and/or Mn⁺⁴include, but are not limited to: phosphono(dithioperoxo)thioic acid, O-phenylphosphono(dithioperoxo)thioic acid, O-benzylphosphono(dithioperoxo)thioic acid, O-cyclohexylphosphono(dithioperoxo)thioic acid, O-norbornylphosphono(dithioperoxo)thioic acid, O,P-diphenylphosphono(dithioperoxo)thioic acid, O,P-dibenzylphosphono(dithioperoxo)thioic acid, O,P-dicyclohexylphosphono(dithioperoxo)thioic acid, and O,P-dinorbornylphosphono(dithioperoxo)thioic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #34: Examples of phosphono(dithioperoxo)dithioic acids, bis[phosphono(dithioperoxo)dithioic acids], poly[phosphono(dithioperoxo)dithioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphono(dithioperoxo)dithioic acid, S-phenylphosphono(dithioperoxo)dithioic acid, S-benzylphosphono(dithioperoxo)dithioic acid, S-cyclohexylphosphono(dithioperoxo)dithioic acid, S-norbornylphosphono(dithioperoxo)dithioic acid, S,P-diphenylphosphono(dithioperoxo)dithioic acid, S,P-dibenzylphosphono(dithioperoxo)dithioic acid, S,P-dicyclohexylphosphono(dithioperoxo)dithioic acid, and S,P-dinorbornylphosphono(dithioperoxo)dithioic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S Valence Stabilizer #35: Examples of S-(alkylthio)thiocarboxylic acids, S-(arylthio)thiocarboxylic acids, and S,S-thiobisthiocarboxylic Acids (S—S Bidentates and S—S Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: (methylthio)thioacetic acid; (methylthio)thiobenzoic acid; (methylthio)thionicotinic acid; (methylthio)thionapthoic acid; (phenylthio)thioacetic acid; (phenylthio)thiobenzoic acid; (phenylthio)thionaphthoic acid; (norbornylthio)thioacetic acid; (norbornylthio)thiobenzoic acid; (norbornylthio)thionapthoic acid; thiobisthioacetic acid; thiobisthiobenzoic acid; and thiobisthionapthoic acid.

S Valence Stabilizer #36: Examples of S-(alkyldisulfido)thiocarboxylic acids, S-(aryldisulfido)thiocarboxylic acids, and S,S′-disulfidobisthiocarboxylic acids (S—S Bidentates and S—S Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: (methyldisulfido)thioacetic acid; (methyldisulfido)thiobenzoic acid; (methyldisulfido)thionicotinic acid; (methyldisulfido)thionapthoic acid; (phenyldisulfido)thioacetic acid; (phenyldisulfido)thiobenzoic acid; (phenyldisulfido)thionaphthoic acid; (norbornyldisulfido)thioacetic acid; (norbornyldisulfido)thiobenzoic acid; (norbornyldisulfido)thionapthoic acid; S,S′-disulfidobisthioacetic pacid; S,S′-disulfidobisthiobenzoic acid; and S,S′-disulfidobisthionapthoic acid.

S Valence Stabilizer #37: Examples of 1,2-dithiolates, bis(1,2-dithiolates), and poly(1,2-dithiolates) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,3-butanedithiol; 1,2-diphenyl-1,2-ethanedithiol; 1,2-di(pentafluorophenyl)-1,2-ethanedithio; 1,2-dicyclohexyl-1,2-ethanedithiol; 1,2-dinorbornyl-1,2-ethanedithiol; 2,3-dimercaptopropanol; 2,3-dimercaptosuccinic acid; poly[bis(arylthio)acetylene]s; and poly[bis(alkylylthio)acetylene]s.

S Valence Stabilizer #38: Examples of rhodanines and bis(rhodanines) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-methylrhodanine; 3-ethylrhodanine; 3-isopropylrhodanine; 3-phenylrhodanine; 3-benzylrhodanine; 3-cyclohexylrhodanine; 3-norbornylrhodanine; 5-methylrhodanine; 5-ethylrhodanine; 5-isopropylrhodanine; 5-phenylrhodanine; 5-benzylrhodanine; 5-cyclohexylrhodanine; 5-norbornylrhodanine; 3,3′-ethylenebisrhodanine; 3,3′-propylenerhodanine; 3,3′-butylenerhodanine; 5,5′-ethylenebisrhodanine; 5,5′-propylenerhodanine; and 5,5′-butylenerhodanine. [Note: rhodanines and bis(rhodanines) tend to stabilize lower oxidation states in metal ions.]

S Valence Stabilizer #39: Examples of dithiocarbimates, bis(dithiocarbimates), and poly(dithiocarbimates) (S—S Bidentates, S—S Tridentates, and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methyldithiocarbimate; trifluoromethyldithiocarbimate; ethyldithiocarbimate; propyldithiocarbimate; isopropyldithiocarbimate; butyldithiocarbimate; tertbutyldithiocarbimate; cyanodithiocarbimate (CDC); cyanamidodithiocarbimate; azidodithiocarbimate; phenyldithiocarbimate; pentafluorophenyldithiocarbimate; benzyldithiocarbimate; naphthyldithiocarbimate; cyclohexyldithiocarbimate; norbornyldithiocarbimate; and adamantyldithiocarbimate. [Note: Carbimates tend to stabilize lower oxidation states in metal ions.]

S Valence Stabilizer #40: Examples of thioxanthates, bis(thioxanthates), and poly(thioxanthates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methyl thioxanthate (MeSxan); ethyl thioxanthate (EtSxan); isopropyl thioxanthate (iPrSxan); trifluoromethyl thioxanthate (CF₃Sxan); cyanothioxanthate; cyanamidothioxanthate; phenyl thioxanthate (PhSxan); benzyl thioxanthate (BzSxan); pentafluorophenyl thioxanthate; cyclohexyl thioxanthate (cHxSxan); and norbornyl thioxanthate. [Note: Thioxanthates tend to stabilize lower oxidation states in metal ions.]

S Valence Stabilizer #41: Examples of xanthates, bis(xanthates), and poly(xanthates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methyl xanthate (Mexan); ethyl xanthate (Etxan); isopropyl xanthate (iPrxan); trifluoromethyl xanthate (CF₃xan); cyanoxanthate; cyanamidoxanthate; phenyl xanthate (Phxan); benzyl xanthate (Bzxan); pentafluorophenyl xanthate; cyclohexyl xanthate (cHxxan); and norbornyl xanthate. [Note: Xanthates tend to stabilize lower oxidation states in metal ions.]

S Valence Stabilizer #42: Examples of phosphinodithioformates (S—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trimethylphosphinodithioformate; triethylphosphinodithioformate; triphenylphosphinodithioformate; tricyclohexylphosphinodithioformate; dimethylphosphinodithioformate; diethylphosphinodithioformate; diphenylphosphinodithioformate; and dicyclohexylphosphinodithioformate.

S Valence Stabilizer #43: Examples of alkyl- and aryl-dithioborates, trithioborates, perthioborates, bis(dithioborates), bis(trithioborates), and bis(perthioborates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: S,O-diethyl dithioborate; S,O-diisopropyl dithioborate; S,O-diphenyl dithioborate; S,O-dibenzyl dithioborate; S,O-dicyclohexyl dithioborate; S,O-dinorbornyl dithioborate; diethyl trithioborate; diisopropyl trithioborate; diphenyl trithioborate; dibenzyl trithioborate; dicyclohexyl trithioborate; and dinorbornyl trithioborate.

S Valence Stabilizer #44: Examples of alkyl- and aryl-dithioboronates and bis(dithioboronates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diethyl dithioboronate; diisopropyl dithioboronate; diphenyl dithioboronate; dibenzyl dithioboronate; dicyclohexyl dithioboronate; and dinorbornyl dithioboronate. [Note: boronates tend to stabilize lower oxidation states in metal ions.]

S Valence Stabilizer #45: Examples of trithioarsonic acids (arsonotrithioic acids), dithioarsonic acids (arsonodithioic acids), tetrathioarsonic acids (arsonotetrathioic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithioarsonic acid, O-phenyltrithioarsonic acid, O-benzyltrithioarsonic acid, O-cyclohexyltrithioarsonic acid, O-norbornyltrithioarsonic acid, O,S-diphenyltrithioarsonic acid, O,S-dibenzyltrithioarsonic acid, O,S-dicyclohexyltrithioarsonic acid, O,S-dinorbornyltrithioarsonic acid; dithioarsonic acid, O-phenyldithioarsonic acid, O-benzyldithioarsonic acid, O-cyclohexyldithioarsonic acid, O-norbornyldithioarsonic acid, O,O-diphenyldithioarsonic acid, O,O-dibenzyldithioarsonic acid, O,O-dicyclohexyldithioarsonic acid, and O,O-dinorbornyldithioarsonic acid.

S Valence Stabilizer #46: Examples of trithioantimonic acids (stibonotrithioic acids), dithioantimonic acids (stibonodithioic acids), tetrathioantimonic acids (stibonotetrathioic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: trimethyltrithioantimonate; triethyltrithioantimonate; and triphenyltrithioantimonate.

S Valence Stabilizer #47: Examples of phosphine P-sulfides and amino-substituted phosphine sulfides (S Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trimethylphosphine sulfide (TMPS); triethylphosphine sulfide (TEPS); triphenylphosphine sulfide (TPhPS); tribenzylphosphine sulfide (TBzPS); tricyclohexylphosphine sulfide (TcHxPS); and trinorbornylphosphine sulfide for phosphine P-sulfides; and tris(dimethylamino)phosphine sulfide; trimorpholinophosphine sulfide; tripiperidinophosphine sulfide; tripyrrolidinophosphine sulfide; and tri(cyclohexylamino)phosphine sulfide for amino-substituted phosphine sulfides.

S Valence Stabilizer #48: Examples of arsine As-sulfides and amino-substituted arsine sulfides (S Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trimethylarsine sulfide; triethylarsine sulfide; triphenylarsine sulfide; tribenzylarsine sulfide; tricyclohexylarsine sulfide; and trinorbornylarsine sulfide for arsine As-sulfides; and tris(dimethylamino)arsine sulfide; trimorpholinoarsine sulfide; tripiperidinoarsine sulfide; tripyrrolidinoarsine sulfide; and tri(cyclohexylamino)arsine sulfide for amino-substituted arsine sulfides.

S Valence Stabilizer #49: Examples of thiolates that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiophenol; naphthalenethiol; 1-dodecanethion; hexadecyl mercaptan; benzenethiol (bt); polybenzenethiols; and polythioarylenes.

S Valence Stabilizer #50: Examples of sulfide that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: sulfides (—S²⁻); disulfides (—S₂ ²⁻); and polysulfides (—S_x ²⁻).

P Valence Stabilizer #1: Examples of monophosphines (P monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, tricyclohexylphosphine, phenyldimethylphosphine, phenyldiethylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, phosphirane, phosphetane, phospholane, phosphorinane, benzophospholane, benzophosphorinane, dibenzophospholane, dibenzophosphorinane, naphthophospholane, naphthophosphorinane, phosphinonorbornane, and phosphinoadamantane.

P Valence Stabilizer #2: Examples of diphosphines (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphospholane, benzodiphospholane, naphthodiphospholane, diphosphorinane, benzodiphosphorinane, dibenzodiphosphorinane, naphthodiphosphorinane, bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane, bis(diphenylphosphino)butane, bis(diphenylphosphino)pentane, 1,2-bis(dipbenylphosphino)ethylene, and o-phenylenebis(diphenylphosphine). (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

P Valence Stabilizer #3: Examples of triphosphines (P monodentates, P—P bidentates, or P—P tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: triphosphorinane, P,P′-tetraphenyl-2-methyl-2-(P-diphenyl)phosphinomethyl-1,3-propanediphosphine; P,P-[2-(P-diphenyl)phosphinoethyl]diethyl-P-phenylphosphine; P,P-[2-(P-diphenyl)phosphino]diphenyl-P-phenylphosphine; and hexahydro-2,4,6-trimethyl-1,3,5-triphosphazine. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

P Valence Stabilizer #4: Examples of tetraphosphines (P monodentates, P—P bidentates, P—P tridentates, and P—P tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: P,P′-tetraphenyl-2,2-[(P-diphenyl)phosphinomethyl]-1,3-propanediphosphine; tri[o-(P-diphenyl)phosphinophenyl]phosphine; and 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

P Valence Stabilizer #5: Examples of pentaphosphines (P monodentates, P—P bidentates, P—P tridentates, and P—P tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-[2-(P-diphenyl)phosphinoethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraphosphadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

P Valence Stabilizer #6: Examples of hexaphosphines (P—P bidentates, P—P tridentates, P—P tetradentates, and P—P hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,1,10,10-tetraphenyl-4,7-[2-(P,P-diphenyl)phosphinoethyl]-1,4,7,10-tetraphosphadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

P Valence Stabilizer #7a: Examples of 5-membered heterocyclic rings containing one phosphorus atom (P monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1-phospholene, 2-phospholene, 3-phospholene, phosphole, oxaphosphole, thiaphosphole, benzophospholene, benzophosphole, benzoxaphosphole, benzothiaphosphole, dibenzophospholene, dibenzophosphole, naphthophospholene, naphthophosphole, naphthoxaphosphole, naphthothiaphosphole.

P Valence Stabilizer #7b: Examples of 5-membered heterocyclic rings containing two phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphospholene, diphosphole, oxadiphospholene, thiadiphospholene, benzodiphospholene, benzodiphosphole, naphthodiphospholene, and naphthodiphosphole.

P Valence Stabilizer #7c: Examples of 5-membered heterocyclic rings containing three phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: triphosphole.

P Valence Stabilizer #8a: Examples of 6-membered heterocyclic rings containing one phosphorus atom (P monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphorin, oxaphosphorin, thiaphosphorin, benzophosphorin, benzoxaphosphorin, benzothiaphosphorin, acridophosphine, phosphanthridine, dibenzoxaphosphorin, dibenzothiaphosphorin, naphthophosphorin, naphthoxaphosphorin, and naphthothiaphosphorin.

P Valence Stabilizer #8b: Examples of 6-membered heterocyclic rings containing two phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: o-diphosphorin, m-diphosphorin, p-diphosphorin, oxadiphosphorin, thiadiphosphorin, benzodiphosphorin, benzoxadiphosphorin, benzothiadiphosphorin, dibenzodiphosphorin, dibenzoxadiphosphorin, dibenzothiadiphosphorin, naphthodiphosphorin, naphthoxadiphosphorin, and naphthothiadiphosphorin.

P Valence Stabilizer #8c: Examples of 6-membered heterocyclic rings containing three phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,3,5-triphosphorin, 1,2,3-triphosphorin, benzo-1,2,3-triphosphorin, and naphtho-1,2,3-triphosphorin.

P Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(P-phenylphosphino)-1-phospholene; 2,5-(P-phenylphosphino)-phospholene; 2-(P-phenylphosphino)-3-phospholene; 2,5-(P-phenylphosphino)-3-phospholene; 2-(P-phenylphosphino)phosphole; 2,5-(P-phenylphosphino)phosphole; 2-(P-phenylphosphino)benzophosphole; 7-(P-phenylphosphino)benzophosphole; and 1,8-(P-phenylphosphino)dibenzophosphole.

P Valence Stabilizer #9b: Examples of 5-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(P-phenylphosphino)-1,3-diphospholene; 2,5-(P-phenylphosphino)-1,3-diphospholene; 2-(P-phenylphosphino)-1,3-diphosphole; 2,5-(P-phenylphosphino)-1,3-diphosphole; 2-(P-phenylphosphino)benzodiphosphole; and 7-(P-phenylphosphino)benzodiphosphole.

P Valence Stabilizer #9c: Examples of 5-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(P-phenylphosphino)-1,3,4-triphosphole; and 2,5-(P-phenylphosphino)-1,3,4-triphosphole.

P Valence Stabilizer #10a: Examples of 6-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(P-phenylphosphino)phosphorin; 2,5-(P-phenylphosphino)phosphorin; 2-(P-phenylphosphino)benzophosphorin; 7-(P-phenylphosphino)benzophosphorin; and 1,9-(P-phenylphosphino)acridophosphine.

P Valence Stabilizer #10b: Examples of 6-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(P-phenylphosphino)-4-diphosphorin; 2,6-(P-phenylphosphino)-4-diphosphorin; 2,3,5,6-(P-phenylphosphino)-4-diphosphorin; 2-(P-phenylphosphino)benzo-1,4-diphosphorin; 2,3-(P-phenylphosphino)benzo-1,4-diphosphorin; 2,8-(P-phenylphosphino)benzo-1,4-diphosphorin; 2,3,5,8-(P-phenylphosphino)benzo-1,4-diphosphorin; 1,9-(P-phenylphosphino)dibenzodiphosphorin; and 1,4,6,9-(P-phenylphosphino)dibenzodiphosphorin.

P Valence Stabilizer #10c: Examples of 6-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(P-phenylphosphino)-1,3,5-triphosphorin; 2,6-(P-phenylphosphino)-1,3,5-triphosphorin; 4-(P-phenylphosphino)-1,2,3-triphosphorin; and 8-(P-phenylphosphino)benzo-1,2,3-triphosphorin.

P Valence Stabilizer #11a: Examples of 5-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1-phospholene; 2,2′,2″-tri-1-phospholene; 2,2′-bi-3-phospholene; 2,2′, 2″-tri-3-phospholene; 2,2′-biphosphole; 2,2′,2″-triphosphole; and 2,2′-bibenzophosphole.

P Valence Stabilizer #11b: Examples of 5-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,3-diphospholene; 2,2′-bi-1,3-diphosphole; and 2,2′-bibenzo-1,3-diphosphole.

P Valence Stabilizer #11c: Examples of 5-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,3,4-triphosphole; and 2,2′,2″-tri-1,3,4-triphosphole.

P Valence Stabilizer #12a: Examples of 6-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-biphosphorin; 2,2′,2″-triphosphorin; 2,2′,2″,2′″-tetraphosphorin; 2,2′-bibenzophosphorin; and 8,8′-bibenzophosphorin.

P Valence Stabilizer #12b: Examples of 6-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3,3′-bi-1,2-diphosphorin; 3,3′,3″-tri-1,2-diphosphorin; 2,2′-bi-1,4-diphosphorin; 2,2′,2″-tri-1,4-diphosphorin; 3,3′-bibenzo-1,2-diphosphorin; 8,8′-bibenzo-1,2-diphosphorin; 2,2′-bibenzo-1,4-diphosphorin; and 8,8′-bibenzo-1,4-diphosphorin.

P Valence Stabilizer #12c: Examples of 6-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,3,5-triphosphorin; 2,2′,2″-tri-1,3,5-triphosphorin; 4,4′-bi-1,2,3-triphosphorin; 4,4′-bibenzo-1,2,3-triphosphorin; and 8,8′-bibenzo-1,2,3-triphosphorin.

P Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: P,P-diphenyldiphosphacyclobutane ([4]aneP₂); P,P-diphenyldiphosphacyclopentane ([5]aneP₂); P,P-diphenyldiphosphacyclohexane ([6]aneP₂); P,P-diphenyldiphosphacycloheptane ([7]aneP₂); P,P-diphenyldiphosphacyclooctane ([8]aneP₂); P,P-diphenyldiphosphacyclobutene ([4]eneP₂); P,P-diphenyldiphosphacyclopentene ([5]eneP₂); P,P-diphenyldiphosphacyclohexene ([6]eneP₂); P,P-diphenyldiphosphacycloheptene ([7]eneP₂); and P,P-diphenyldiphosphacyclooctene ([8]eneP₂).

P Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: P,P,P-triphenyltriphosphacyclohexane ([6]aneP₃); P,P,P-triphenyltriphosphacycloheptane ([7]aneP₃); P,P,P-triphenyltriphosphacyclooctane ([8]aneP₃); P,P,P-triphenyltriphosphacyclononane ([9]aneP₃); P,P,P-triphenyltriphosphacyclodecane ([10]aneP₃); P,P,P-triphenyltriphosphacycloundecane ([11]aneP₃); P,P,P-triphenyltriphosphacyclododecane ([12]aneP₃); P,P,P-triphenyltriphosphacyclohexatriene ([6]trieneP₃); P,P,P-triphenyltriphosphacycloheptatriene ([7]trieneP₃); P,P,P-triphenyltriphosphacyclooctatriene ([8]trieneP₃); P,P,P-triphenyltriphosphacyclononatriene ([9]trieneP₃); P,P,P-triphenyltriphosphacyclodecatriene ([10]trieneP₃); P,P,P-triphenyltriphosphacycloundecatriene ([11]trieneP₃); and P,P,P-triphenyltriphosphacyclododecatriene ([12]trieneP₃).

P Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: P,P,P,P-tetraphenyltetraphosphacyclooctane ([8]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclononane ([9]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclodecane ([10]aneP₄); P,P,P,P-tetraphenyltetraphosphacycloundecane ([11]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclododecane ([12]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclotridecane ([13]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclotetradecane ([14]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclopentadecane ([15]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclohexadecane ([16]aneP₄); P,P,P,P-tetraphenyltetraphosphacycloheptadecane ([17]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclooctadecane ([18]aneP₄); P,P,P,P-tetraphenyltetraphosphacyclononadecane ([19]aneP₄); and P,P,P,P-tetraphenyltetraphosphacycloeicosane ([20]aneP₄).

P Valence Stabilizer #13d: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tridentates, or P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: P,P,P,P,P-pentaphenylpentaphosphacyclodecane ([10]aneP₅); P,P,P,P,P-pentaphenylpentaphosphacycloundecane ([11]aneP₅); P,P,P,P,P-pentaphenylpentaphosphacyclododecane ([12]aneP₅); P,P,P,P,P-pentaphenylpentaphosphacyclotridecane ([13]aneP₅); P,P,P,P,P-pentaphenylpentaphosphacyclotetradecane ([14]aneP₅); and P,P,P,P,P-pentaphenylpentaphosphacyclopentadecane ([15]aneP₅).

P Valence Stabilizer #13e: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P—P Tridentates, P—P—P—P Tetradentates, or P—P—P—P—P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: P,P,P,P,P,P-hexaphenylhexaphosphacyclododecane ([12]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclotridecane ([13]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclotetradecane ([14]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclopentadecane ([15]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclohexadecane ([16]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacycloheptadecane ([17]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclooctadecane ([18]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclononadecane ([19]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacycloeicosane ([20]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacycloheneicosane ([21]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclodocosane ([22]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclotricosane ([23]aneP₆); P,P,P,P,P,P-hexaphenylhexaphosphacyclotetracosane ([24]aneP₆).

P Valence Stabilizer #13f: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclohexadecane ([16]aneP₈); P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloheptadecane ([17]aneP₈); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclooctadecane ([18]aneP₈); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclononadecane ([19]aneP₈); P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloeicosane ([20]aneP₈); P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloheneicosane ([21]aneP₈); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclodocosane ([22]aneP₈); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotricosane ([23]aneP₈); and P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotetracosane ([24]aneP₈).

P Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in component 5-membered heterocyclic rings (P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetraphospholenes; tetraphospholes; tetraoxaphospholes; tetradiphospholenes; tetradiphospholes; and tetraoxadiphospholes.

P Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in component 5-membered heterocyclic rings (P—P Tetradentates and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexaphospholenes; hexaphospholes; hexaoxaphospholes; hexadiphospholenes; hexadiphospholes; and hexaoxadiphospholes.

P Valence Stabilizer #14c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in component 5-membered heterocyclic rings (P—P Tridentates; P—P Tetradentates; or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: octaphospholenes; octaphospholes; octaoxaphospholes; octadiphospholenes; octadiphospholes; and octaoxadiphospholes.

P Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphatetraphospholenes; tetraphosphatetraphospholenes; dipbosphatetraphospholes; tetraphosphatetraphospholes; diphoshatetradiphospholes; and tetraphosphatetradiphospholes.

P Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphahexaphospholenes; triaphosphahexaphospholenes; diphosphahexaphospholes; triphosphahexaphospholes; diphoshahexadiphospholes; and triphosphahexadiphospholes.

P Valence Stabilizer #15c:—Examples of eight membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphaoctaphospholenes; tetraphosphaoctaphospholenes; diphosphaoctaphospholes; tetraphosphaoctaphospholes; diphoshaoctadiphospholes; and tetraphosphaoctadiphospholes.

P Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in component 6-membered heterocyclic rings (P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclotetraphosphorins; cyclotetraaoxaphosphorins; cyclotetradiphosphorins; and cyclotetraoxadiphosphorins.

P Valence Stabilizer #16b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in component 6-membered heterocyclic rings (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: cyclohexaphosphorins; cyclohexaoxaphosphorins; cyclohexadiphosphorins; and cyclohexaoxadiphosphorins.

P Valence Stabilizer #16c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in component 6-membered heterocyclic rings (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclooctaphosphorins; cyclooctaoxaphosphorins; cyclooctadiphosphorins; and cyclooctaoxadiphosphorins.

P Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in a combination of 6-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphacyclotetraphosphorins; tetraphosphacyclotetraphosphorins; diphosphacyclotetraoxaphosphorins; tetraphosphacyclotetraoxaphosphorins; diphosphacyclotetradiphosphorins; tetraphosphacyclotetradiphosphorins; diphosphacyclotetraoxadiphosphorins; and tetraphosphacyclotetraoxadiphosphorins.

P Valence Stabilizer #17b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in a combination of 6-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphacyclohexaphosphorins; triphosphacyclohexaphosphorins; diphosphacyclohexaoxaphosphorins; triphosphacyclohexaoxaphosphorins; diphosphacyclohexadiphosphorins; triphosphacyclohexadiphosphorins; diphosphacyclohexaoxadiphosphorins; and triphosphacyclohexaoxadiphosphorins.

P Valence Stabilizer #17c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in a combination of 6-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphacyclooctaphosphorins; tetraphosphacyclooctaphosphorins; diphosphacyclooctaoxaphosphorins; tetraphosphacyclooctaoxaphosphorins; diphosphacyclooctadiphosphorins; -tetraphosphacyclooctadiphosphorins; diphosphacyclooctaoxadiphosphorins; and tetraphospbacyclooctaoxadiphosphorins.

O Valence Stabilizer #1: Examples of dithioperoxydicarbonic acids, bis(dithioperoxydicarbonic acids), poly(dithioperoxydicarbonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithioperoxydicarbonic acid, O-phenyldithioperoxydicarbonic acid; O-benzyldithioperoxydicarbonic acid; O-cyclohexyldithioperoxydicarbonic acid; O-norbornyldithioperoxydicarbonic acid; O,O′-diphenyldithioperoxydicarbonic acid; O,O′-dibenzyldithioperoxydicarbonic acid; O,O′-dicyclohexyldithioperoxydicarbonic acid; and O,O′-dinorbornyldithioperoxydicarbonic acid.

O Valence Stabilizer #2: Examples of imidodiphosphonic acids, hydrazidodiphosphonic acids, bis(imidodiphosphonic acids), bis(hydrazidodiphosphonic acids), poly(imidodiphosphonic acids), poly(hydrazidodiphosphonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: imidodiphosphonic acid, methylimidodiphosphonic acid, isopropylimidodiphosphonic acid, tert-butylimidodiphosphonic acid, phenylimidodiphosphonic acid, pentafluorophenylimidodiphosphonic acid, benzylimidodiphosphonic acid, cyclohexylimidodiphosphonic acid, norbornylimidodiphosphonic acid, dimethylimidodiphosphonic acid, diisopropylimidodiphosphonic acid, di-tert-butylimidodiphosphonic acid, diphenylimidodiphosphonic acid, di-pentafluorophenylimidodiphosphonic acid, dibenzylimidodiphosphonic acid, dicyclohexylimidodiphosphonic acid, and dinorbornylimidodiphosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

O Valence Stabilizer #3: Examples of imidodiphosphonamides, hydrazidodiphosphonamides, bis(imidodiphosphonamides), bis(hydrazidodiphosphonamides), poly(imidodiphosphonamides), and poly(hydrazidodiphosphonamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to imidodiphosphonamide, N-methylimidodiphosphonamide, N-isopropylimidodiphosphonamide, N-tert-butylimidodiphosphonamide, N-phenylimidodiphosphonamide, N-pentafluorophenylimidodiphosphonamide, N-benzylimidodiphosphonamide, N-cyclohexylimidodiphosphonamide, N-norbornylimidodiphosphonamide, N,N′″-dimethylimidodiphosphonamide, N,N′″-diisopropylimidodiphosphonamide, N,N′″-di-tert-butylimidodiphosphonamide, N,N′″-diphenylimidodiphosphonamide, N,N′″-di-pentafluorophenylimidodiphosphonamide, N,N′″-dibenzylimidodiphosphonamide, N,N′″-dicyclohexylimidodiphosphonamide, and N,N′″-dinorbornylimidodiphosphonamide. [Note: The phosphite (p+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

O Valence Stabilizer #4: Examples of diphosphonamides, bis(diphosphonamides), and poly(diphosphonamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphosphonamide, N-methyldiphosphonamide, N-isopropyldiphosphonamide, N-tert-butyldiphosphonamide, N-phenyldiphosphonamide, N-pentafluorophenyldiphosphonamide, N-benzyldiphosphonamide, N-cyclohexyldiphosphonamide, N-norbornyldiphosphonamide, N,N′″-dimethyldiphosphonamide, N,N′″-diisopropyldiphosphonamide, N,N′″-di-tert-butyldiphosphonamide, N,N′″-diphenydiphosphonamide, N,N′″-di-pentafluorophenyldiphosphonamide, N,N′″-dibenzyldiphosphonamide, N,N′″-dicyclohexyldiphosphonamide, and N,N″-dinorbornyldiphosphonamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

O Valence Stabilizer #5: Examples of carbonates and bis(carbonates) (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: carbonate; bicarbonate; O,O-diethylcarbonate; diisopropylcarbonate; diphenylcarbonate; dibenzylcarbonate; dicyclohexylcarbonate; and dinorbornylcarbonate.

O Valence Stabilizer #6: Examples of carbazates (carbazides), bis(carbazates), and poly(carbazates) (O—OBidentates, O-O-Tridentates, and O—O Tetradentates; or possibly N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-dimethylcarbazate; N,N′-di(trifluoromethyl)carbazate; N,N′-diethylcarbazate; N,N′-diphenylcarbazate; N,N′-dibenzylcarbazate; N,N′-di(pentafluorophenyl)carbazate; N,N′-dicyclohexylcarbazate; and N,N′-dinorbornylcarbazate.

O Valence Stabilizer #7: Examples of arsonic acids, bis(arsonic acids), poly(arsonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: arsonic acid, O-phenylarsonic acid, O-benzylarsonic acid, O-cyclohexylarsonic acid, O-norbornylarsonic acid, O,O-diphenylarsonic acid, O,O-dibenzylarsonic acid, O,O-dicyclohexylarsonic acid, O,O-dinorbornylarsonic acid; and aminophenylarsonic acids.

O Valence Stabilizer #8: Examples of alkyl- and aryl-borates and bis(borates) (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: triethyl borate; diisopropyl borate; diphenyl borate; dibenzyl borate; dicyclohexyl borate; and dinorbornyl borate.

O Valence Stabilizer #9: Examples of alkyl- and aryl-boronates and bis(boronates) (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diethyl boronate; diisopropyl boronate; diphenyl boronate; dibenzyl boronate; dicyclohexyl boronate; and dinorbornyl boronate. [Note: boronates tend to stabilize lower oxidation states in metal ions.]

O Valence Stabilizer #10: Examples of phosphine P-oxides and amino-substituted phosphine oxides (O Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trimethylphosphine oxide (TMPO); triethylphosphine oxide (TEPO); triphenylphosphine oxide (TPhPO); tribenzylphosphine oxide (TBzPO); tricyclohexylphosphine oxide (TcHxPO); and trinorbornylphosphine oxide for phosphine P-oxides; and hexamethylphosphoramide (HMPA); trimorpholinophosphine oxide (TMrPO); tripiperidinophosphine oxide; tripyrrolidinophosphine oxide; and tri(cyclohexylamino)phosphine oxide for amino-substituted phosphine oxides.

O Valence Stabilizer #11: Examples of arsine As-oxides and amino-substituted arsine oxides (O Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trimethylarsine oxide (TMAsO); triethylarsine oxide (TEAsO); triphenylarsine oxide (TPhAsO); tribenzylarsine oxide (TBzAsO); tricyclohexylarsine oxide (TcHxAsO); and trinorbornylarsine oxide for arsine As-oxides; and hexamethylarsonamide; trimorpholinoarsine oxide; tripiperidinoarsine oxide; tripyrrolidinoarsine oxide; and tri(cyclohexylamino)arsine oxide for amino-substituted arsine oxides.

O Valence Stabilizer #12a: Examples of 5-membered heterocyclic rings containing one oxygen atom (O monodentate) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: furan, dihydrofuran, oxazole, isoxazole, oxadiazole, oxatriazole, oxathiole, benzofuran, benzodihydrofuran, benzoxazole, benzisoxazole, benzoxadiazole (benzofurazan), dibenzofuran, dibenzoxazole, dibenzisoxazole, naphthofuran, naphthoxazole, naphthisoxazole, and naphthoxadiazole.

O Valence Stabilizer #12b: Examples of 5-membered heterocyclic rings containing two oxygen atoms (O monodentate or O—O bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dioxolane, benzodioxolane, and naphthodioxolane.

O Valence Stabilizer #13a: Examples of 6-membered heterocyclic rings containing one oxygen atom (O monodentate) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydropyran, pyran, oxazine, oxadiazine, oxatriazine, oxathiin, benzopyran, benzoxazine, benzoxadiazine, dibenzopyran, naphthopyran, naphthoxazine, and naphthoxadiazine.

O Valence Stabilizer #13b: Examples of 6-membered heterocyclic rings containing two oxygen atoms (O monodentate or O—O bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydrodioxane, dioxane, benzodioxane, dibenzodioxane, and naphthodioxane.

O Valence Stabilizer #14a: Examples of 5-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,5-dihydroxy-2,5-dihydrofuran; 2,5-bis(hydroxymethyl)-2,5-dihydrofuran; 2,5-bis(2-hydroxyphenyl)-2,5-dihydrofuran; 2,5-dihydroxyfuran; 2,5-bis(hydroxymethyl)furan; and 2,5-bis(2-hydroxyphenyl)furan.

O Valence Stabilizer #14b: Examples of 5-membered heterocyclic rings containing two oxygen atoms and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-hydroxy-1,3-dioxolane; 2-hydroxymethyl)-1,3-dioxolane; 4,5-dihydroxy-1,3-dioxolane; 4,5-bis(2-hydroxyphenyl)-1,3-dioxolane; 2-hydroxybenzodioxolane; and 7-hydroxybenzodioxolane.

O Valence Stabilizer #15a: Examples of 6-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,6-dihydroxy-2,5-dihydropyran; 2,6-bis(hydroxymethyl)-2,5-dihydropyran; 2,6-bis(2-hydroxyphenyl)-2,5-dihydropyran; 2,6-dihydroxypyran; 2,6-bis(hydroxymethyl)pyran; 2,6-bis(2-hydroxyphenyl)pyran; 2-hydroxy-1-benzopyran; 8-hydroxy-1-benzopyran; and 1,9-dihydroxydibenzopyran.

O Valence Stabilizer #15b: Examples of 6-membered heterocyclic rings containing two oxygen atoms and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band”.valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-hydroxy-1,4-dioxane; 2,6-dihydroxy-1,4-dioxane; 2,6-bis(2-hydroxyphenyl)-1,4-dioxane; 2,3-dihydroxy-1,4-benzodioxane; 5,8-dihydroxy-1,4-benzodioxane; 1,8-dihydroxydibenzodioxane; and 1,4,5,8-tetrahydroxydibenzodioxane.

O Valence Stabilizer #16a: Examples of 5-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-2,5-dihydrofuran; 2,2′,2″-tri-2,5-dihydrofuran; 2,2′-bifuran; 2,2′,2″-trifuran; 1,1′-bis(dibenzofuran); and polyfurans.

O Valence Stabilizer #16b: Examples of 5-membered heterocyclic rings containing two oxygen atoms and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,3-dioxolane; 4,4′-bi-1,3-dioxolane; 7,7′-bi-1,2-benzodioxolane; and 3,3′-bi-1,2-benzodioxolane.

O Valence Stabilizer #17a: Examples of 6-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-2,5-dihydropyran; 2,2′,2″-tri-2,5-dihydropyran; 2,2′-bipyran; 2,2′,2″-tripyran; and 1,1′-bis(dibenzopyran).

O Valence Stabilizer #17b: Examples of 6-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-1,4-dioxane; 2,2′-bi-1,3-dioxane; 5,5′-bi-1,4-benzodioxane; and 2,2′-bi-1,3-benzodioxane.

O Valence Stabilizer #18a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 8-crown-4; 10-crown-4; 12-crown-4; 14-crown-4; 16-crown-4; 18-crown-4; 20-crown-4; dibenzo-8-crown-4; dibenzo-10-crown-4; dibenzo-12-crown-4; dibenzo-14-crown-4; dibenzo-16-crown-4; dibenzo-18-crown-4; dibenzo-20-crown-4; tetrabenzo-8-crown-4; tetrabenzo-10-crown-4; tetrabenzo-12-crown-4; tetrabenzo-14-crown-4; tetrabenzo-16-crown-4; tetrabenzo-18-crown-4; and tetrabenzo-20-crown-4.

O Valence Stabilizer #18b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 10-crown-5; 15-crown-5; 20-crown-5; 25-crown-5; pentabenzo-10-crown-5; pentabenzo-15-crown-5; pentabenzo-20-crown-5; and pentabenzo-25-crown-5.

O Valence Stabilizer #18c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 12-crown-6; 18-crown-6; 24-crown-6; 30-crown-6; 36-crown-6; tribenzo-12-crown-6; tribenzo-18-crown-6; tribenzo-24-crown-6; tribenzo-30-crown-6; tribenzo-36-crown-6; hexabenzo-12-crown-6; hexabenzo-18-crown-6; hexabenzo-24-crown-6; hexabenzo-30-crown-6; and hexabenzo-36-crown-6.

O Valence Stabilizer #18d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 14-crown-7; 21-crown-7; 28-crown-7; 35-crown-7; heptabenzo-14-crown-7; heptabenzo-21-crown-7; heptabenzo-28-crown-7; and heptabenzo-35-crown-7.

O Valence Stabilizer #18e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 16-crown-8; 24-crown-8; 32-crown-8; 40-crown-8; 48-crown-8; tetrabenzo-16-crown-8; tetrabenzo-24-crown-8; tetrabenzo-32-crown-8; tetrabenzo-40-crown-8; tetrabenzo-48-crown-8; octabenzo-16-crown-8; octabenzo-24-crown-8; octabenzo-32-crown-8; octabenzo-40-crown-8; and octabenzo-48-crown-8.

O Valence Stabilizer #18f: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 20-crown-10; 30-crown-10; 40-crown-10; 50-crown-10; pentabenzo-20-crown-10; pentabenzo-30-crown-10; pentabenzo-40-crown-10; and pentabenzo-50-crown-10.

O Valence Stabilizer #19: Examples of four-, five-, six-, seven-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen and are contained in component 5-membered heterocyclic rings (O—O Bidentates, O-O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrafurans, tetrabenzofurans; pentafurans; pentabenzofurans; hexafurans; hexabenzofurans; heptafurans; heptabenzofurans; octafurans; octabenzofurans; decafurans; and decabenzofurans.

O Valence Stabilizer #20: Examples of four-, five-, six-, seven-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen and are contained in component 6-membered heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetrapyrans, tetrabenzopyrans; pentapyrans; pentabenzopyans; hexapyans; hexabenzopyans; heptapyans; heptabenzopyans; octapyans; octabenzopyans; decapyans; and decabenzopyans.

N—S Valence Stabilizer #1: Examples of thioimidates, dithioimidates, polythioimidates, and derivatives of thioimidic acid (N—S bidentates and N—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: S-methyl formathioimidate; S-ethyl formathioimidate; S-methyl acetathioimidate; S-ethyl acetathioimidate; S-methyl benzthioimidate; S-ethyl benzthioimidate; S-methyl cyclohexylthioimidate; S-ethyl cyclohexylthioimidate; S-methyl pentafluorobenzthioimidate; S-ethyl pentafluorobenzthioimidate; S-methyl 2-pyridylthioimidate; S-ethyl 2-pyridylthioimidate; S,S′-dimethyl benzdithioimidate; S,S′-dimethyl tetrafluorobenzdithioimidate; 2-iminothiolane; and 2-iminotetrahydrothiopyran. [Note: Many thioimidate complexes are decomposed by water, but their stability can be enhanced through the use of fluorinated solubility control anions (e.g. PF₆ ⁻).]

N—S Valence Stabilizer #2: Examples of thioguanylureas, guanidinothioureas, bis(thioguanylureas), bis(guanidinothioureas, pQly(thioguanylureas), and poly(guanidinothioureas) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thioguanylurea (amidinothiourea); guanidinothiourea; methylthioguanylurea; ethylthioguanylurea; isopropylthioguanylurea; butylthioguanylurea; benzylthioguanylurea; phenylthioguanylurea; tolylthioguanylurea; naphthylthioguanylurea; cyclohexylthioguanylurea; norbornylthioguanylurea; adamantylthioguanylurea; dimethylthioguanylurea; diethylthioguanylurea; diisopropylthioguanylurea; dibutylthioguanylurea; dibenzylthioguanylurea; diphenylthioguanylurea; ditolylthioguanylurea; dinaphthylthioguanylurea; dicyclohexylthioguanylurea; dinorbornylthioguanylurea; diadamantylthioguanylurea; ethylenebis(thioguanylurea); propylenebis(thioguanylurea); phenylenebis(thioguanylurea); piperazinebis(thioguanylurea); oxalylbis(thioguanylurea); malonylbis(thioguanylurea); succinylbis(thioguanylurea); and phthalylbis(thioguanylurea). [Note: thioguanylureas generally tend to favor lower oxidation states in complexed metals.]

N—S Valence Stabilizer #3: Examples of amidinothioamides, guanidinothioamides, bis(amidinothioamides), bis(guanidinothioamides), poly(amidinothioamides), and poly(guanidinothioamides) (including both N-amidinothioamides and 2-amidinothioacetamides) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: amidinothioacetamide; guanidinothioamide, amidinothiopropanamide; amidinothiobutanamide; amidinothiobenzamide; amidinothiotoluamide; amidinothiocyclohexamide; N-methylamidinothioacetamide; N-ethylamidinothiopropanamide; N-propylamidinothiobutanamide; N-phenylamidinothiobenzamide; N-tolylamidinothiotoluamide; N-cyclohexylamidinothiocyclohexamide; bis(amidinothiooxamide); bis(amidinothiomalonamide); bis(amidinothiosuccinamide); bis(amidinothiophthalamide); 2-amidinothioacetamide (thiomalonamamidine); N-methyl-2-amidinothioacetamide; N-ethyl-2-amidinothioacetamide; N-phenyl-2-amidinothioacetamide; N-benzyl-2-amidinothioacetamide; N-cyclohexyl-2-amidinothioacetamide; N,N′-dimethyl-2-amidinothioacetamide; N,N′-diethyl-2-amidinothioacetamide; N,N′-diphenyl-2-amidinothioacetamide; N,N′-dibenzyl-2-amidinothioacetamide; and N,N′-dicyclohexyl-2-amidinothioacetamide. [Note: amidinothioamides generally tend to favor lower oxidation states in complexed metals.]

N—S Valence Stabilizer #4: Examples of imidoylthioamides, bis(imidoylthioamides), and poly(imidoylthioamides); (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: acetimidoylthioacetamide; acetimidoylthiopropanamide; acetimidoylthiobutanamide; acetimidoylthiobenzamide; acetimidolylthiotoluamide; acetimidoylthiocyclohexamide; propimidoylthiopropanamide; butimidoylthiobutanamide; benzimidoylthiobenzamide; ethylenebis(acetimidoylthioacetamide); propylenebis(acetimidoylthioacetamide); and phenylenebis(acetimidoylthioacetamide). [Note: imidoylthioamides generally tend to favor lower oxidation states in complexed metals.]

N—S Valence Stabilizer #5: Examples of thioureas, bis(thioureas), and poly(thioureas), including thiourylene complexes (N—S bidentates and N—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiourea; methylthiourea; ethylthiourea; isopropylthiourea; benzylthiourea; phenylthiourea; cyclohexylthiourea; naphthylthiourea (ntu); biphenylthiourea; norbornylthiourea; adamantylthiourea; N,N′-dimethylthiourea; N,N′-diethylthiourea; N,N′-diisopropylthiourea; N,N′-dibenzylthiourea; N,N′-dicyclohexylthiourea; N,N′-dinapthylthiourea; N,N′-dibiphenylthiourea; N,N′-dinorbornylthiourea; N,N′-diadamantylthiourea; tetramethylthiourea; ethylenethiourea (2-imidazolidinethione)(etu); 4,5-dihydroxy-2-imidazolinethione (dhetu); propylenethiourea; N-(thiazol-2-yl)thiourea; diphenylphosphinothioyl thioureas; allylthiourea; N-allyl-N′-pyridylthiourea; N-allyl-N′-anisylthiourea; N-allyl-N′-naphthylthiourea; N-allyl-N′-phenylthiourea; thioglycoluril (acetylenethiourea); and bis(pyridylmethyl)thiourea. [Note: thioureas generally tend to favor lower oxidation states in complexed metals.]

N—S Valence Stabilizer #6: Examples of thiocarboxamides, bis(thiocarboxamides), and poly(thiocarboxamides), (N—S bidentates, N—S tridentates, and N—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiocarbamide (tu); thioacetamide (taa); thiopropionamide; thiobutanamide; thiobenzamide (1-pbenylthioformamide)(tba); 1-naphthylthioformamide; 1-cyclohexylthioformamide); 1-norbornylthioformamide; 1-adamantylthioformamide; N,N-dimethylthioformamide; N,N-dimethylthioacetamide; pyridine-2-thiocarboxamide (thiopicolinamide); pyrazine-2,3-dithiocarboxamide; thionicotinamide; 2-thiophenethiocarhoxamide; N N-dimethylthiobenzamide; N-ethylthiocarbamide (N-etu); tetramethylthiocarbamide (tmtu); 2-thioacetamidothiazole (tatz); and polythioacrylamides. [Note: thiocarboxamides generally tend to favor lower oxidation states in complexed metals.]

N—S Valence Stabilizer #7: Examples of imidosulfurous diamides and bis(imidosulfurous diamides) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-diphenylimidosulfurous diamide; N,N′-dibenzylimidosulfurous diamide; and phenylenebis(imidosulfurous diamide). [Note: These complexes tend to hydrolyze unless stabilized with a fluorinated anionic solubility control agent. The sulfite (S⁺⁴) valence of the sulfur atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N—S Valence Stabilizer #8: Examples of sulfurdiimines, bis(sulfurdiimines), and poly(sulfurdiimines) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-diphenylsulfurdiimine; N,N′-dibenzylsulfurdiimine; and phenylenebis(sulfurdiimine). [Note: These complexes tend to hydrolyze unless stabilized with a fluorinated anionic solubility control agent. The sulfite (S⁺⁴) valence of the sulfur atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N—S Valence Stabilizer #9: Examples of phosphonimidothioic acid, phosphonimidodithioic acid, bis(phosphonimidothioic acid); bis(phosphonimidodithioic acid), and derivatives thereof (N—S Bidentates, N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphonimidothioic acid, phosphonimidodithioic acid; O-phenylphosphonimidothioic acid; O-benzylphosphonimidothioic acid; O-cyclohexylphosphonimidothioic acid; O-norbornylphosphonimidothioic acid; S-phenylphosphonimidodithioic acid; S-benzylphosphonimidodithioic acid; S-cyclohexylphosphonimidodithioic acid; and S-norbornylphosphonimidodithioic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N—S Valence Stabilizer #10: Examples of phosphonothioic diamides, bis(phosphonothioic diamides), and poly(phosphonothioic diamides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphonothioic diamide, phosphonothioic dihydrazide, phosphonamidothioic hydrazide, N-phenylphosphonothioic diamide, N-benzylphosphonothioic diamide, N-cyclohexylphosphonothioic diamide, and N-norbornylphosphonothioic diamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N—S Valence Stabilizer #11: Examples of phosphonamidothioic acid, phosphonamidiinidodithioic acid, bis(phosphonamidothioic acid), bis(phosphonamidimidodithioic acid), poly(phosphonamidothioic acid), and poly(phosphonamidimidodithioic acid), and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphonamidothioic acid, phosphonamidimidodithioic acid, phosphonohydrazidodithioic acid, phosphonohydrazidothioic acid, S-phenylphosphonamidimidodithioic acid, S-benzylphosphonamidimidodithioic acid, S-cyclohexylphosphonamidimidodithioic acid, and S-norbornylphosphonamidimidodithioic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N—S Valence Stabilizer #12: Examples of beta-aminothiones (N-substituted 3-amino-2-propenethioaldehydes), bis(beta-aminothiones), and poly(beta-aminothiones) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-methylamino-3-penten-2-thione; 4-ethylamino-3-penten-2-thione; 4-isopropyl amino-3-penten-2-thione; 4-phenylamino-3-penten-2-thione; 4-naphthylamino-3-penten-2-thione; 4-cyclohexylamino-3-penten-2-thione; 4-norbornylamino-3-penten-2-thione; 4-hydroxyamino-3-penten-2-thione; 3-methylamino-1-phenyl-2-butenethioaldehydel; 3-ethylamino-1-phenyl-2-butenethioaldehyde; 3-isopropylamino-1-phenyl-2-butenethioaldehyde; 3-phenylamino-1-phenyl-2-butenethioaldehyde; 3-naphthylamino-1-phenyl-2-butenethioaldehyde; 3-cyclohexylamino-1-phenyl-2-butenethioaldehyde; 3-norbornylamino-1-phenyl-2-butenethioaldehyde; 3-hydroxyamino-1-phenyl-2-butenethioaldehyde; 3-phenylamino-1,3-diphenyl-2-propenethioaldehyde; 3-cyclohexylamino-1,3-dicyclohexyl-2-propenethioaldehyde; and 3-norbornylamino-1,3-dinorbornyl-2-propenethioaldehyde.

N—S Valence Stabilizer #13: Examples of 3-aminothioacrylamides (3-amino-2-thiopropenamides), 3,3-diaminothioacrylamides, bis(3-aminothioacrylamides), bis(3,3-diaminothioacrylamides), poly(3-aminothioacrylamides), and poly(3,3-diaminothioacrylamides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-methylaminothioacryl amide; 3-ethylaminothioacrylamide, 3-i sopropyl aminothioacryl amide, 3-phenylaminothioacrylamide; 3-naphthylaminothioacrylamide; 3-cyclohexylaminothioacrylamide; 3-norbornylaminothioacrylamide; 3-hydroxyaminothioacrylamide; N—ethyl-3-methylaminothioacrylamide; N-ethyl-3-ethylaminothioacrylamide, N-isopropyl-3-isopropylaminothioacrylamide, N-phenyl-3-phenylaminothioacrylamide; N-naphthyl-3-naphthylaminothioacrylamide; N-cyclohexyl-3-cyclohexylaminothioacrylamide; N-norbornyl-3-norbornylaminothioacrylamide; 3-amino-3-methylaminothioacrylamide; 3-amino-3-ethylaminothioacrylamide, 3-amino-3-isopropylaminothioacrylamide, 3-amino-3-phenylaminothioacrylamide; 3-amino-3-naphthylaminothioacrylamide; 3-amino-3-cyclohexylaminothioacrylamide; 3-amino-3-norbornylaminothioacrylamide; and 3-amino-3-hydroxyaminothioacrylamide.

N—S Valence Stabilizer #14: Examples of 3-aminothioacrylic acids (3-amino-2-thiopropenoic acids), 3-mercapto-3-aminothioacrylic acids, bis(3-aminothioacrylic acids), bis(3-mercapto-3-aminothioacrylic acids), poly(3-aminothioacrylic acids), and poly(3-mercapto-3-aminothioacrylic acids), and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-aminothioacrylic acid; 3-mercapto-3-aminothioacrylic acid; 3-methylaminothioacrylic acid; 3-ethylaminothioacrylic acid; 3-isopropylaminothioacrylic acid; 3-phenylaminothioacrylic acid; 3-naphthylaminothioacrylic acid; 3-cyclohexylaminothioacrylic acid; 3-norbornylaminothioacrylic acid; 3-hydroxyaminothioacrylic acid; methyl 3-methylaminothioacrylate; ethyl 3-ethylaminothioacrylate; isopropyl 3-isopropylaminothioacrylate; benzyl 3-phenylaminothioacrylate; naphthyl 3-naphthylaminothioacrylate; cyclohexyl 3-cyclohexylaminothioacrylate; and norbornyl 3-norbornylaminothioacryl ate.

N—S Valence Stabilizer #15: Examples of N-thioacyl benzylidenimines, bis(N-thioacyl benzylidenimines), and poly(N-thioacyl benzylidenimines) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-thioformyl benzylidenimine, N-thioacetyl benzylidenimine; N-thiobenzoyl benzylidenimine; and N-pentafluorothiobenzoyl benzylidenimine.

N—S Valence Stabilizer #16: Examples of thiocarbonyl oximes, bis(thiocarbonyl oximes), and poly(thiocarbonyl oximes) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: butane-3-thione-2-one monoxime); and diphenylethane-2-thione-1-one monoxime.

N—S Valence Stabilizer #17: Examples of mercapto oximes, bis(mercapto oximes), and poly(mercapto oximes) (including 2-sulfur heterocyclic oximes) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-mercaptobutan-2-one oxime; 4-mercaptohexan-3-one oxime; (1,2-diphenyl-2-mercaptoethanone oxime); 1,2-di(trifluoromethyl)-2-mercaptoethanone oxime; 1,2-dicyclohexyl-2-mercaptoethanone oxime; 1,2-dinorbornyl-2-mercaptoethanone oxime; 2-mercaptobenzaldehyde oxime; 2-mercapto-1-naphthaldehyde oxime; thiophene-2-aldoxime; methyl 2-thiophenyl ketoxime; and phenyl 2-thiophenyl ketoxime.

N—S Valence Stabilizer #18: Examples of 2-nitrothiophenols (2-nitrobenzenethiols) (N—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-nitrothiophenol; 2,3-dinitrothiophenol; 2,4-dinitrothiophenol; 2,5-dinitrothiophenol; 2,6-dinitrothiophenol; 1-nitro-2-naphthalenethiol; and 2-nitro-1-naphthalenethiol.

N—S Valence Stabilizer #19: Examples of 2-nitrilothiophenols (2-nitrilobenzenethiols) (N—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-cyanothiophenol; 2,3-dicyanothiophenol; 2,4-dicyanothiophenol; 2,5-dicyanothiophenol; 2,6-dicyanothiophenol; 1-cyano-2-naphthalenethiol; and 2-cyano-1-naphthalenethiol.

N—S Valence Stabilizer #20: Examples of thiohydrazides, bis(thiohydrazides), and poly(thiohydrazides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thioformic hydrazide; thioacetic hydrazide; thiopropionic hydrazide; thiobenzoic hydrazide; thiophthalhydrazide; thiosalicylic hydrazide; thionaphthoic hydrazides; thionorbornaneacetic hydrazide; thionicotinic hydrazide; and thioisonicotinic hydrazide. [Note: Thiohydrazides prefer complexation with lower oxidation states in metal ions.]

N—S Valence Stabilizer #21: Examples of thiosemicarbazides, bis(thiosemicarbazides), and poly(thiosemicarbazides) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiosemicarbazide (tsc); thiosemicarbazide diacetic acid (tsda); 1-methylthiosemicarbazide (1 mts); 1-ethylthiosemicarbazide; 1-isopropylthiosemicarbazide; 1-phenylthiosemicarbazide (1 pts)(cryogenine); 1-benzylthiosemicarbazide; 1-cyclohexylthiosemicarbazide; 1-norbornylthiosemicarbazide; 4-methylthiosemicarbazide (4mts); 4-ethylthiosemicarbazide; 4-isopropylthiosemicarbazide; 4-phenylthiosemicarbazide (4-pts); 4-benzylthiosemicarbazide; 4-cyclohexylthiosemicarbazide; 4-norbornylthiosemicarbazide; nicotinic thiosemicarbazide; isonicotinic thiosemicarbazide; and 4-phenyl-1-benzenesulfonyl-3-thiosemicarbazide (pbst). [Note: Thiosemicarbazides prefer complexation with lower oxidation states in metal ions.]

N—S Valence Stabilizer #22: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or sulfur (usually thiols, mercaptans, or thiocarbonyls) and are not contained in component heterocyclic rings (N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: triazadithiacyclodecane ([10]aneS₂N₃); triazadithiacycloundecane ([11]aneS₂N₃); triazadithiacyclododecane ([12]aneS₂N₃); triazadithiacyclotridecane ([13]aneS₂N₃); triazadithiacyclotetradecane ([14]aneS₂N₃); triazadithiacyclopentadecane ([15]aneS₂N₃); thiomorpholine; and thiazolidine.

N—S Valence Stabilizer #23: Examples of five- or seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in component heterocyclic rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiopyrantripyridines; dithiophenetripyrroles; trithiopyrantetrapyridines; and trithiophenetetrapyrroles.

N—S Valence Stabilizer #24: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in a combination of heterocyclic rings and amine, imine, thiol, mercapto, or thiocarbonyl groups (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azathiapentaphyrins; diazadithiapentaphyrins; azathiapentaphyrins; and diazadithiapentaphyrins.

N—O Valence Stabilizer #1: Examples of imidates, diimidates, polyimidates, and derivatives of imidic acid (N—O bidentates and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: O-methyl formimidate; O-ethyl formimidate; O-methyl acetimidate; O-ethyl acetimidate; O-methyl benzimidate; O-ethyl benzimidate; O-methyl cyclohexylimidate; O-ethyl cyclohexylimidate; O-methyl pentafluorobenzimidate; O-ethyl pentafluorobenzimidate; O-methyl 2-pyridylimidate; O-ethyl 2-pyridylimidate; O,O′-dimethyl benzdiimidate; O,O′-dimethyl tetrafluorobenzdiimidate; 2-iminotetrahydrofuran; and 2-iminotetrahydropyran. [Note: Most imidate complexes are decomposed by water, but their stability can be enhanced through the use of fluorinated solubility control anions (e.g. PF₆ ⁻).]

N—O Valence Stabilizer #2: Examples of pseudoureas, bis(pseudoureas), and poly(pseudoureas) (N—O bidentates and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: O-methyl pseudourea; O-ethyl pseudourea; O-isopropyl pseudourea; O-benzyl pseudourea; O-cyclohexyl pseudourea; O-norbornyl pseudourea; O-pentafluorobenzyl pseudourea; N-methyl pseudourea; N-ethyl pseudourea; N-isopropyl pseudourea; N-benzyl pseudourea; N-cyclohexyl pseudourea; N-norbornyl pseudourea; and N-pentafluorobenzyl pseudourea.

N—O Valence Stabilizer #3: Examples of 2-amidinoacetates, bis(2-amidinoacetates), and poly(2-amidinoacetates) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-methyl-2-amidinoacetate; O-methyl-2-amidinoacetate; N-benzyl-2-amidinoacetate; and O-benzyl-2-amidinoacetate. [Note: many 2-amidinoacetates tend to hydrolyze in water. This can be minimized through the use of fluorinated solubility control anions such as PF₆ ⁻.]

N—O Valence Stabilizer #4: Examples of ureas, bis(ureas), and poly(ureas), including urylene complexes (N—O bidentates and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: urea; methylurea; ethylurea; isopropylurea; benzylurea; cyclohexylurea; naphthylurea; biphenylurea; norbornylurea; adamantylurea; N,N′-dimethylurea; N,N′-diethylurea; N,N′-diisopropylurea; N,N′-dibenzylurea; N,N′-dicyclohexylurea; N,N′-dinapthylurea; N,N′-dibipbenylurea; N,N′-dinorbornylurea; N,N′-diadamantylurea; ethyleneurea (2-imidazolidone); propyleneurea; glycoluril (acetyleneurea); and N,N′-bis(4-nitrophenyl)urea.

N—O Valence Stabilizer #5: Examples of phosphonimidic-acid, bis(phosphonimidic acid), poly(phosphonimidic acid), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphonimidic acid; O-phenylphosphonimidic acid; O-benzylphosphonimidic acid; O-cyclohexylphosphonimidic acid; and O-norbornylphosphonimidic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N—O Valence Stabilizer #6: Examples of phosphonamidic acid, phosphonic diamide, bis(phosphonamidic acid), bis(phosphonic diamide), poly(phosphonamidic acid), poly(phosphonic diamide), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphonamidic acid, phosphonic diamide, phosphonamidic hydrazide, phosphonic dihydrazide, O-phenylphosphonamidic acid, O-benzylphosphonamidic acid, O-cyclohexylphosphonamidic acid, O-norbornylphosphonamidic acid, N-benzylphosphonic diamide, N-phenylphosphonic diamide, N-cyclohexylphosphonic diamide, and N-norbornylphosphonic diamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

N—O Valence Stabilizer #7: Examples of beta-ketoamines (N-substituted 3-amino-2-propenals), bis(beta-ketoamines), and poly(beta-ketoamines) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-methylamino-3-penten-2-one; 4-ethylamino-3-penten-2-one; 4-isopropylamino-3-penten-2-one; 4-phenylamino-3-penten-2-one; 4-naphthylamino-3-penten-2-one; 4-cyclohexylamino-3-penten-2-one; 4-norbornylamino-3-penten-2-one; 4-hydroxyamino-3-penten-2-one; 3-methylamino-1-phenyl-2-butenal; 3-ethylamino-1-phenyl-2-butenal; 3-isopropylamino-1-phenyl-2-butenal; 3-phenylamino-1-phenyl-2-butenal; 3-naphthylamino-1-phenyl-2-butenal; 3-cyclohexylamino-1-phenyl-2-butenal; 3-norbornylamino-1-phenyl-2-butenal; 3-hydroxyamino-1-phenyl-2-butenal; 3-phenylamino-1,3-diphenyl-2-propenal; 3-cyclohexylamino-1,3-dicyclohexyl-2-propenal; 3-norbornylamino-1,3-dinorbornyl-2-propenal; 2,2′-pyridil; alpha-pyridoin; 4-aminoantipyrine (aap); beta-phenylaminopropiophenone; and polyaminoquinones (PAQs).

N—O Valence Stabilizer #8: Examples of 3-aminoacrylamides (3-amino-2-propenamides), 3,3-diaminoacrylamides, bis(3-aminoacrylamides), bis(3,3-diaminoacrylamides), poly(3-aminoacrylamides), and poly(3,3-diaminoacrylamides) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-methylaminoacrylamide; 3-ethylaminoacrylamide, 3-isopropylaminoacrylamide, 3-phenylaminoacrylamide; 3-naphthylaminoacrylamide; 3-cyclohexylaminoacrylamide; 3-norbornylaminoacrylamide; 3-hydroxyaminoacrylamide; N-methyl-3-methylaminoacrylamide; N-ethyl-3-ethylaminoacrylamide, N-isopropyl-3-isopropylaminoacrylamide, N-phenyl-3-phenylaminoacrylamide; N-naphthyl-3-naphthylaminoacrylamide; N-cyclohexyl-3-cyclohexylaminoacrylamide; N-norbornyl-3-norbornylaminoacrylamide; 3-amino-3-methylaminoacrylamide; 3-amino-3-ethylaminoacrylamide, 3-amino-3-isopropylaminoacrylamide, 3-amino-3-phenylaminoacrylamide; 3-amino-3-naphthylaminoacrylamide; 3-amino-3-cyclohexylaminoacrylamide; 3-amino-3-norbornylaminoacrylamide; and 3-amino-3-hydroxyaminoacrylamide.

N—O Valence Stabilizer #9: Examples of 3-aminoacrylic acids (3-amino-2-propenoic acids), 3-hydroxy-3-aminoacrylic acids, bis(3-aminoacrylic acids), bis(3-hydroxy-3-aminoacrylic acids), poly(3-aminoacrylic acids), and poly(3-hydroxy-3-aminoacrylic acids), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3-aminoacrylic acid; 3-hydroxy-3-aminoacrylic acid; 3-methylaminoacrylic acid; 3-ethylaminoacrylic acid; 3-isopropylaminoacrylic acid; 3-phenylaininoacrylic acid; 3-naphthylaminoacrylic acid; 3-cyclohexylaminoacrylic acid; 3-norbornylaminoacrylic acid; 3-hydroxyaminoacrylic acid; methyl 3-methylaminoacrylate; ethyl 3-ethylaminoacrylate; isopropyl 3-isopropylaminoacrylate; benzyl 3-phenylaminoacrylate; naphthyl 3-naphthylaminoacrylate; cyclohexyl 3-cyclohexylaminoacrylate; and norbornyl 3-norbornyl aminoacryl ate.

N—O Valence Stabilizer #10: Examples of N-acyl benzylidenimines, bis(N-acyl benzylidenimines), and poly(N-acyl benzylidenimines) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-formyl benzylidenimine, N-acetyl benzylidenimine; N-benzoyl benzylidenimine; and N-pentafluorobenzoyl benzylidenimine.

N—O Valence Stabilizer #11: Examples of 2-nitroanilines (N—O Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: 2-nitroaniline; 2,6-dintroaniline; 2-nitrophenylenediamine; 2-nitrophenylenetriamine; 2-nitro-1-aminonaphthalene; 1-nitro-2-aminonaphthalene; nitrodiaminonaphthalene; and dipicrylamine.

N—O Valence Stabilizer #12: Examples of 2-nitrilophenols (N—O Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-cyanophenol; 2,3-dicyanophenol; 2,4-dicyanophenol; 2,5-dicyanophenol; 2,6-dicyanophenol; 1-cyano-2-naphthol; and 2-cyano-1-naphthol. Also includes acylcyanamides.

N—O Valence Stabilizer #13: Examples of amine N-oxides and N-diazine oxides (azoxy compounds) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: pyridine N-oxide (pyNO or PNO); picoline N-oxide (picNO); lutidine N-oxide (lutNO or LNO); collidine N-oxide (collNO or CNO); quinoline N-oxide (QuinNO or QNO); isoquinoline N-oxide (isoQuinNO or IQNO); acridine N-oxide (AcrNO or ANO); picolinic acid N-oxide (PicANO); pyridinethiolate N-oxide (PTNO); adenine N-oxide; adenosine N-oxide; 1,10-phenanthroline mono-N-oxide (phenNO); 1,10-phenanthroline N,N-dioxide (phen2NO); bipyridyl mono-N-oxide (bipyNO); bipyridyl N,N-dioxide (bipy2NO); pyrazine mono-N-oxide (pyzNO); pyrazine N,N-dioxide (pyz2NO); pyrimidine mono-N-oxide (pymNO); pyrimidine N,N-dioxide (pym2NO); pyridazine mono-N-oxide (pdzNO); pyridazine N,N-dioxide (pdz2NO); quinoxaline mono-N-oxide (qxNO); quinoxaline N,N-dioxide (qx2NO); phenazine mono-N-oxide (phzNO); phenazine N,N-dioxide (phz2NO); 2,3-di(pyridine N-oxide)quinoxaline (dpoq); inosine N-oxide; 4,4′-bipyridine N,N-dioxide; 1-hydroxypyrazole 2-oxide; 1-hydroxyimidazole 3-oxide; 2,2′-diimidazyl 3,-3′-dioxide; imidazole N-oxides; lIhydroxyimidazole-3-N-oxides; N-benzylidine aniline N-oxide; N-(naphthylidene) aniline N-oxide; N-(hydroxybenzylidene) aniline N-oxide; and 2,2′-dibenzimidazyl 3,3′-dioxide (indigo N,N-dioxide) for amine N-oxides; and azoxybenzene; phthalazine N-oxide; benzocinnoline N-oxide; and bipyrazinyl N-oxide as N-diazine oxide examples.

N—O Valence Stabilizer #14: Examples of hydrazides, bis(hydrazides), and poly(hydrazides) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: formic hydrazide; acetic hydrazide; propionic hydrazide; benzoic hydrazide; phthalhydrazide; salicylic hydrazide; naphthoic hydrazides; norbornaneacetic hydrazide; nicotinic hydrazide; and isonicotinic hydrazide (isoniazid). [Note: Hydrazides prefer complexation with lower oxidation states in metal ions.]

N—O Valence Stabilizer #15: Examples of semicarbazides, bis(semicarbazides), and poly(semicarbazides) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: semicarbazide (sc); semicarbazide diacetic acid (sda); 1-methylsemicarbazide; 1-ethylsemicarbazide; 1-isopropylsemicarbazide; 1-phenylsemicarbazide; 1-benzylsemicarbazide; 1-cyclohexylsemicarbazide; 1-norbornylsemicarbazide; 4-methylsemicarbazide; 4-ethylsemicarbazide; 4-isopropylsemicarbazide; 4-phenylsemicarbazide; 4-benzylsemicarbazide; 4-cyclohexylsemicarbazide; 4-norbornylsemicarbazide; nicotinic semicarbazide; and isonicotinic semicarbazide. [Note: Semicarbazides prefer complexation with lower oxidation states in metal ions.]

N—O Valence Stabilizer #16: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or oxygen (usually hydroxy, carboxy, or carbonyl groups) and are not contained in component heterocyclic rings (N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺ include, but are not limited to: triazadioxacyclodecane ([10]aneO₂N₃); triazadioxacycloundecane ([11]aneO₂N₃); triazadioxacyclododecane ([12]aneO₂N₃); triazadioxacyclotridecane ([13]aneO₂N₃); triazadioxacyclotetradecane ([14]aneO₂N₃); and triazadioxacyclopentadecane ([15]aneO₂N₃).

N—O Valence Stabilizer #17: Examples of five- or seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in component heterocyclic rings (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dipyrantripyridines; difurantripyrroles; tripyrantetrapyridines; and trifurantetrapyrroles.

N—O Valence Stabilizer #18: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in a combination of heterocyclic rings and amine, imine, hydroxy, carboxy, or carbonyl groups (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azaoxapentaphyrins; diazadioxapentaphyrins; azaoxapentaphyrins; and diazadioxapentaphyrins.

S—O Valence Stabilizer #1: Examples of thiobiurets (thioimidodicarbonic diamides), thioisobiurets, thiobiureas, thiotriurets, thiotriureas, bis(thiobiurets), bis(thioisobiurets), bis(thiobiureas), poly(thiobiurets), poly(thioisobiurets), poly(thiobiureas) (S—O Bidentates, S—O Tridentates, S—O Tetradentates), and (3-formamidino thiocarbamides) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiobiuret, thioisobiuret, thiobiurca, thiotriuret, thiotriurea, nitrothiobiuret, dinitrothiobiuret, aminothiobiuret, diaminothiobiuret, oxythiobiuret, dioxythiobiuret, cyanothiobiuret, methylthiobiuret, ethylthiobiuret, isopropylthiobiuret, phenylthiobiuret, benzylthiobiuret, cyclohexylthiobiuret, norbornylthiobiuret, adamantylthiobiuret, dimethylthiobiuret, diethylthiobiuret, dicyclohexylthiobiuret, dinorbornylthiobiuret, and diadamantylthiobiuret.

S—O Valence Stabilizer #2: Examples of acylthioureas, aroylthioureas, thioacylureas, thioaroylureas, bis(acylthioureas), bis(aroylthioureas), bis(thioacylureas) bis(thioaroylureas), poly(thioacylthioureas), poly(thioaroylthioureas), poly(thioacylureas), and poly(thioaroylureas) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thioformylurea, thioacetylurea, thiobenzoylurea, thiocyclohexoylurea, pentafluorothiobenzoylurea, acetylthiourea, benzoylthiourea, and cyclohexoylthiourea.

S—O Valence Stabilizer #3: Examples of thioimidodialdehydes, thiohydrazidodialdehydes (thioacyl hydrazides), bis(thioimidodialdehydes), bis(thiohydrazidodialdehydes), poly(thioimidodialdehydes), and poly(thiohydrazidodialdehydes) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiodiacetamide, thiodipropanamide, thiodibutanamide, thiodibenzamide, and thiodicyclohexamide.

S—O Valence Stabilizer #4: Examples of thioimidodicarbonic acids, thiohydrazidodicarbonic acids, bis(thioimidodicarbonic acids), bis(thiohydrazidodicarbonic acids), poly(thioimidodicarbonic acids), poly(thiohydrazidodicarbonic acids) and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thioimidodicarbonic acid, thiohydrazidodicarbonic acid, O-phenylthioimidodicarbonic acid, O-benzylthioimidodicarbonic acid, O-cyclohexylthioimidodicarbonic acid, O-norbornylthioimidodicarbonic acid, O,O′-diphenylthioimidodicarbonic acid, O,O′-dibenzylthioimidodicarbonic acid, O,O′-dicyclohexylthioimidodicarbonic acid, O,O′-dinorbornylthioimidodicarbonic acid.

S—O Valence Stabilizer #5: Examples of 1,2-monothioketones (monothiolenes, monothio-alpha-ketonates), 1,2,3-monothioketones, 1,2,3-dithioketones, monothiotropolonates, ortho-monothioquinones, bis(1,2-monothioketones), and poly(1,2-monothioketones) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiotropolone; 1,2-monothiobenzoquinone (o-monothioquinone); di-tert-butyl-1,2-monothiobenzoquinone; hexafluoro-1,2-monothiobenzoquinone; 1,2-monothionaphthoquinone; 9,10-monothiophenanthroquinone; monothiosquaric acid; monothiodeltic acid; monothiocroconic acid; and monothiorhodizonic acid.

S—O Valence Stabilizer #6: Examples of trithioperoxydicarbonic diamides, bis(trithioperoxydicarbonic diamides), and poly(trithioperoxydicarbonic diamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: trithioperoxydicarbonic diamide; N-phenyltrithioperoxydicarbonic diamide; N-benzyltrithioperoxydicarbonic diamide; N-cyclohexyltrithioperoxydicarbonic diamide; N-norbornyltrithioperoxydicarbonic diamide; N,N′-diphenyltrithioperoxydicarbonic diamide; N,N′-dibenzyltrithioperoxydicarbonic diamide; N,N′-dicyclohexyltrithioperoxydicarbonic diamide; and N,N′-dinorbornyltrithioperoxydicarbonic diamide.

S—O Valence Stabilizer #7: Examples of dithiodicarbonic acids, bis(dithiodicarbonic acids), poly(dithiodicarbonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodicarbonic acid, O-phenyldithiodicarbonic acid, O-benzyldithiodicarbonic acid, O-cyclohexyldithiodicarbonic acid, O-norbornyldithiodicarbonic acid, O,O′-diphenyldithiodicarbonic acid, O,O′-dibenzyldithiodicarbonic acid, O,O′-dicyclohexyldithiodicarbonic acid, and O,O′-dinorbornyldithiodicarbonic acid.

S—O Valence Stabilizer #8: Examples of trithioperoxydicarbonic acids, bis(trithioperoxydicarbonic acids), poly(trithioperoxydicarbonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: -trithioperoxydicarbonic acid, O-phenyltrithioperoxydicarbonic acid; O-benzyltrithioperoxydicarbonic acid; O-cyclohexyltrithioperoxydicarbonic acid; O-norbornyltrithioperoxydicarbonic acid; O,O′-diphenyltrithioperoxydicarbonic acid; O,O′-dibenzyltrithioperoxydicarbonic acid; O,O′-dicyclohexyltrithioperoxydicarbonic acid; and O,O′-dinorbornyltrithioperoxydicarbonic acid.

S—O Valence Stabilizer #9: Examples of monothioperoxydiphosphoramides, bis(monothioperoxydiphosphoramides), and poly(monothioperoxydiphosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioperoxydiphosphoramide, N-methylmonothioperoxydiphosphoramide, N-isopropylmonothioperoxydiphosphoramide, N-tert-butylmonothioperoxydiphosphoramide, N-phenylmonothioperoxydiphosphoramide, N-pentafluorophenylmonothioperoxydiphosphoramide, N-benzylmonothioperoxydiphosphoramide, N-cyclohexylmonothioperoxydiphosphoramide, N-norbornylmonothioperoxydiphosphoramide, N,N′″-dimethylmonothioperoxydiphosphoramide, N,N′″-diisopropylmonothioperoxydiphosphoramide, N,N′″-di-tert-butylmonothioperoxydiphosphoramide, N,N′″-diphenylmonothioperoxydiphosphoramide, N,N′″-di-pentafluorophenylmonothioperoxydiphosphoramide, N,N′″-dibenzylmonothioperoxydiphosphoramide, N,N′″-dicyclohexylmonothioperoxydiphosphoramide, and N,N′″-dinorbornylmonothioperoxydiphosphoramide.

S—O Valence Stabilizer #10: Examples of monothioperoxydiphosphoric acids, bis(monothioperoxydiphosphoric acids), poly(monothioperoxydiphosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioperoxydiphosphoric acid, methylmonothioperoxydiphosphoric acid, isopropylmonothioperoxydiphosphoric acid, tert-butylmonothioperoxydiphosphoric acid, phenylmonothioperoxydiphosphoric acid, pentafluorophenylmonothioperoxydiphosphoric acid, benzylmonothioperoxydiphosphoric acid, cyclohexylmonothioperoxydiphosphoric acid, norbornylmonothioperoxydiphosphoric acid, dimethylmonothioperoxydiphosphoric acid, diisopropylmonothioperoxydiphosphoric acid, di-tert-butylmonothioperoxydiphosphoric acid, diphenylmonothioperoxydiphosphoric acid, di-pentafluorophenylmonothioperoxydiphosphoric acid, dibenzylmonothioperoxydiphosphoric acid, dicyclohexylmonothioperoxydiphosphoric acid, and dinorbornylmonothioperoxydiphosphoric acid.

S—O Valence Stabilizer #11: Examples of monothioimidodiphosphonic acids, monothiohydrazidodiphosphonic acids, bis(monothioimidodiphosphonic acids), bis(monothiohydrazidodiphosphonic acids), poly(monothioimidodiphosphonic acids), poly(monothiohydrazidodiphosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioimidodiphosphonic acid, methylmonothioimidodiphosphonic acid, isopropylmonothioimidodiphosphonic acid, tert-butylmonothioimidodiphosphonic acid, phenylmonothioimidodiphosphonic acid, pentafluorophenylmonothioimidodiphosphonic acid, benzylmonothioimidodiphosphonic acid, cyclohexylmonothioimidodiphosphonic acid, norbornylmonothioimidodiphosphonic acid, dimethylmonothioimidodiphosphonic acid, diisopropylmonothioimidodiphosphonic acid, di-tert-butylmonothioimidodiphosphonic acid, diphenylmonothioimidodiphosphonic acid, di-pentafluorophenylmonothioimidodiphosphonic acid, dibenzylmonothioimidodiphosphonic acid, dicyclohexylmonothioimidodiphosphonic acid, and dinorbornylmonothioimidodiphosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #12: Examples of monothioimidodiphosphonamides, monothiohydrazidodiphosphonamides, bis(monothioimidodiphosphonamides), bis(monothiohydrazidodiphosphonamides), poly(monothioimidodiphosphonamides), and poly(monothiohydrazidodiphosphonamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioimidodiphosphonamide, N-methylmonothioimidodiphosphonamide, N-isopropylmonothioimidodiphosphonamide, N-tert-butylmonothioimidodiphosphonamide, N-phenylmonothioimidodiphosphonamide, N-pentafluorophenylmonothioimidodiphosphonamide, N-benzylmonothioimidodiphosphonamide, N-cyclohexylmonothioimidodipbosphonamide, N-norbornylmonothioimidodiphosphonamide, N,N′″-dimethylmonothioimidodiphosphonamide, N,N′″-diisopropylmonothioimidodiphosphonamide, N,N′″-di-tert-butylmonothioimidodiphosphonamide, N,N′″-diphenylmonothioimidodiphosphonamide, N,N′″-di-pentafluorophenylmonothioimidodiphosphonamide, N,N′″-dibenzylmonothioimidodiphosphonamide, N,N′″-dicyclohexylmonothioimidodiphosphonamide, and N,N′″-dinorbornylmonothioimidodiphosphonamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #13: Examples of dithiodiphosphonamides, bis(dithiodiphosphonamides), and poly(dithiodiphosphonamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodiphosphonamide, N-methyldithiodiphosphonamide, N-isopropyldithiodiphosphonamide, N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide, N-pentafluorophenyldithiodiphosphonamide, N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide, N-norbornyldithiodiphosphonamide, N,N′″-dimethyldithiodiphosphonami de, N,N′″-diisopropyldithiodiphosphonamide, N,N′″-di-tert-butyldithiodiphosphonamide, N,N′″-diphenyldithiodiphosphonamide, N,N′″-di-pentafluorophenyldithiodiphosphonamide, N,N′″-dibenzyldithiodiphosphonamide, N,N′″-dicyclohexyldithiodiphosphonamide, and N,N′″-dinorbornyldithiodiphosphonamide. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #14: Examples of dithiodiphosphonic acids, bis(dithiodiphosphonic acids), poly(dithiodiphosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiodiphosphonic acid, methyldithiodiphosphonic acid, isopropyldithiodiphosphonic acid, tert-butyldithiodiphosphonic acid, phenyldithiodiphosphonic acid, pentafluorophenyldithiodiphosphonic acid, benzyldthiodiphosphonic acid, cyclohexyldithiodiphosphonic acid norbornyldithiodiphosphonic acid, dimethyldithiodiphosphonic acid, diisopropyldiothiodiphosphonic acid, di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic acid, di-pentafluorophenyldithiodiphosphonic acid, dibenzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphonic acid, and dinorbornyldithiodiphosphoric acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #15: Examples of monothioperoxydiphosphonamides, bis(monothioperoxydiphosphonamides), and poly(monothioperoxydiphosphonamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioperoxydiphosphonamide, N-methylmonothioperoxydiphosphonamide, N-isopropylmonothioperoxydiphosphonamide, N-tert-butylmonothioperoxydiphosphonamide, N-phenylmonothioperoxydiphosphonamide, N-pentafluorophenylmonothioperoxydiphosphonamide, N-benzylmonothioperoxydiphosphonamide, N-cyclohexylmonothioperoxydiphosphonamide, N-norbornylmonothioperoxydiphosphonamide, N,N′″-dimethylmonothioperoxydiphosphonamide, N,N′″-diisopropylmonothioperoxydiphosphonamide, N,N′″-di-tert-butylmonothioperoxydiphosphonamide, N,N′″-diphenylmonothioperoxydiphosphonamide, N,N′″-di-pentafluorophenylmonothioperoxydiphosphonamide, N,N′″-dibenzylmonothioperoxydiphosphonamide, N,N′″-dicyclohexylmonothioperoxydiphosphonamide, and N,N′″-dinorbornylmonothioperoxydiphosphonamide. [Note: The phosphite (p+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #16: Examples of monothioperoxydiphosphonic acids, bis(monothioperoxydiphosphonic acids), poly(monothioperoxydiphosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioperoxydiphosphonic acid, methylmonothioperoxydiphosphonic acid, isopropylmonothiopcroxydiphosphonic acid, tert-butylmonothioperoxydiphosphonic acid, phenylmonothioperoxydiphosphonic acid, pentafluorophenylmonothioperoxydiphosphonic acid, benzylmonothioperoxydiphosphonic acid, cyclohexylmonothioperoxydiphosphonic acid, norbornylmonothioperoxydiphosphonic acid, dimethylmonothioperoxydiphosphonic acid, diisopropylmonothioperoxydiphosphonic acid, di-tert-butylmonothioperoxydiphosphonic acid, diphenylmonothioperoxydiphosphonic acid, di-pentafluorophenylmonothioperoxydiphosphonic acid, dibenzylmonothioperoxydiphosphonic acid, dicyclohexylmonothioperoxydiphosphonic acid, and dinorbornylmonothioperoxydiphosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #17: Examples of monothiophosphoric acids (phosphorothioic acids), bis(monothiophosphoric acids), poly(monothiophosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiophosphoric acid, O-phenylmonothiophosphoric acid, O-benzylmonothiophosphoric acid, O-cyclohexylmonothiophosphoric acid, O-norbornylmonothiophosphoric acid, O,O-diphenylmonothophosphoric acid, O,O-dibenzylmonothiophosphoric acid, O,O-dicyclohexylmonothiophosphoric acid, and O,O-dinorbornylmonothiophosphoric acid.

S—O Valence Stabilizer #18: Examples of phosphoro(dithioperoxoic) acids, bis[phosphoro(dithioperoxoic) acids], poly[phosphoro(dithioperoxoic) acids], and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphoro(dithioperoxoic) acid, O-phenylphosphoro(dithioperoxoic) acid, O-benzylphosphoro(dithioperoxoic) acid, O-cyclohexylphosphoro(dithioperoxoic) acid, O-norbornylphosphoro(dithioperoxoic) acid, O,O-diphenylphosphoro(dithioperoxoic) acid, O,O-dibenzylphosphoro(dithioperoxoic) acid, O,O-dicyclohexylphosphoro(dithioperoxoic) acid, and O,O-dinorbornylphosphoro(dithioperoxoic) acid.

S—O Valence Stabilizer #19: Examples of monothiophosphonic Acids (phosphonothioic acids), bis(monothiophosphonic acids), poly(monothiophosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiophosphonic acid, O-phenylmonothiophosphonic acid, O-benzylmonothiophosphonic acid, β-cyclohexylmonothiophosphonic acid, O-norbornylmonothiophosphonic acid, O,P-diphenylmonothiophosphonic acid, O,P-dibenzylmonothiophosphonic acid, O,P-dicyclohexylmonothiophosphonic acid, and O,P-dinorbornylmonothiophosphonic acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #20: Examples of phosphono(dithioperoxoic) acids, bis[phosphono(dithioperoxoic) acids], poly[phosphono(dithioperoxoic) acids], and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphono(dithioperoxoic) acid, O-phenylphosphono(dithioperoxoic) acid, O-benzylphosphono(dithioperoxoic) acid, O-cyclohexylphosphono(dithioperoxoic) acid, O-norbornylphosphono(dithioperoxoic) acid, O,P-diphenylphosphono(dithioperoxoic) acid, O,P-dibenzylphosphono(dithioperoxoic) acid, O,P-dicyclohexylphosphono(dithioperoxoic) acid, and O,P-dinorbornylphosphono(dithioperoxoic) acid. [Note: The phosphite (P⁺³) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]

S—O Valence Stabilizer #21: Examples of beta-hydroxythioketones, beta-hydroxythioaldehydes, bis(beta-hydroxythioketones), bis(beta-hydroxythioaldehydes), poly(beta-hydroxythioketones), and poly(beta-hydroxythioaldehydes) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-hydroxypentan-2-thione; 1,3-diphenyl-3-hydroxypropanethioaldehyde; 1,3-dibenzyl-3-hydroxypropanethioaldehyde; 1,3-dicyclohexyl-3-hydroxypropanethioaldehyde; 1,3-dinorbornyl-3-hydroxypropanethioaldehyde; 1,3-di(2-thienyl)-3-hydroxypropanethioaldehyde; 1,3-di(2-furyl)-3-hydroxypropanethioaldehyde; 1-hydroxythioacetophenone; and beta-hydroxythiobenzophenone.

S—O Valence Stabilizer #22: Examples of beta-mercaptoketones, beta-mercaptoaldehydes, bis(beta-mercaptoketones), bis(beta-mercaptoaldehydes), poly(beta-mercaptoketones), and poly(beta-mercaptoaldehydes) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-mercaptopentan-2-one; 1,3-diphenyl-3-mercaptopropanal; 1,3-dibenzyl-3-mercaptopropanal; 1,3-dicyclohexyl-3-mercaptopropanal; 1,3-dinorbornyl-3-mercaptopropanal; 1,3-di(2-thienyl)-3-mercaptopropanal; 1,3-di(2-furyl)-3-mercaptopropanal; 3-mercapto-1,5-pentanedialdehyde; o-mercaptoacetophenone; 5-mercapto-1,4-naphthoquinone; 1-mercaptoacridone; 1-mercaptoanthraquinone; 1,8-dimercaptoanthraquinone; and beta-mercaptobenzophenone.

S—O Valence Stabilizer #23: Examples of N-(aminomethylol)thioureas [N-(aminohydroxymethyl)thioureas], bis[N-(aminomethylol)thioureas], and poly[N-(aminomethylol)thioureas] (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N′-(aminohydroxymethyl)thiourea; N,N″-dimethyl-N′-(aminohydroxymethyl)thiourea; N,N′-diethyl-N′-(aminohydroxymethyl)thiourea; N,N″-isopropyl-N′-(aminohydroxymethyl)thiourea; N,N″-diphenyl-N′-(aminohydroxymethyl)thiourea; N,N″-dibenzyl-N′-(aminohydroxymethyl)thiourea; N,N″-dicyclohexyl-N′-(aminohydroxymethyl)thiourea; and N,N″-dinorbornyl-N′-(aminohydroxymethyl)thiourea.

S—O Valence Stabilizer #24: Examples of N-(aminomethylthiol)ureas [N-(aminomercaptomethyl)ureas], bis[N-(aminomethylthiol)ureas], and poly[N-(aminomethylthiol)ureas] (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N′-(aminomercaptomethyl)urea; N,N′-dimethyl-N′-(aminomercaptomethyl)urea; N,N′-diethyl-N′-(aminomercaptomethyl)urea; N,N″-isopropyl-N′-(aminomercaptomethyl)urea; N,N″-diphenyl-N′-(aminomercaptomethyl)urea; N,N″-dibenzyl-N′-(aminomercaptomethyl)urea; N,N″-dicyclohexyl-N′-(aminomercaptomethyl)urea; and N,N″-dinorbornyl-N′-(aminomercaptomethyl)urea.

S—O Valence Stabilizer #25: Examples of monotbiooxamides, bis(monothiooxamides), and poly(monothiooxamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothiooxamide, N-methylthiooxamide; N-ethylthiooxamide; N-isopropylthiooxamide; N-phenylthiooxamide; N-benzylthiooxamide; N-cyclohexylthiooxamide; N-norbornylthiooxamide; N,N′-dimethylthiooxamide; N,N′-diethylthiooxamide; N,N′-diisopropylthiooxamide; N,N′-diphenylthiooxamide; N,N′-dibenzylthiooxamide; N,N′-dicyclohexylthiooxamide; and N,N′-dinorbornylthiooxamide.

S—O Valence Stabilizer #26: Examples of beta-mercapto carboxylic acids, bis(beta-mercapto carboxylic acids), poly(beta-mcrcapto carboxylic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methyl 3-mercaptopropanoate; methyl 3-mercaptobutanoate; ethyl 3-mercaptobutanoate; phenyl 3-mercaptobutanoate; cyclohexyl 3-mercaptobutanoate; norbornyl 3-mercaptobutanoate; methyl beta-mercaptohydrocinnamate; ethyl beta-mercaptohydrocinnamate; phenyl beta-mercaptohydrocinnamate; methyl o-mercaptobenzoate; ethyl o-mercaptobenzoate; phenyl o-mercaptobenzoate; cyclohexyl o-mercaptobenzoate; (2-benzothiazolylthio) succinic acid (mtbs); norbornyl o-mercaptobenzoate; and 3-[(benzothiazol-2-yl)thio]propionic acid.

S—O Valence Stabilizer #27: Examples of beta-mercapto thiocarboxylic acids, bis(beta-mercapto thiocarboxylic acids), poly(beta-mercapto thiocarboxylic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methyl 3-mercaptothiobutanoate; ethyl 3-mercaptothiobutanoate; phenyl 3-mercaptothiobutanoate; cyclohexyl 3-mercaptothiobutanoate; norbornyl 3-mercaptothiobutanoate; methyl beta-mercaptothiocinnamate; ethyl beta-mercaptothiocinnamate; phenyl beta-mercaptothiocinnamate; methyl o-mercaptothiobenzoate; ethyl o-mercaptothiobenzoate; phenyl o-mercaptothiobenzoate; cyclohexyl o-mercaptothiobenzoate; norbornyl o-mercaptothiobenzoate; and (alkylthio)oxoethyl alkyl(aryl) disulfides.

S—O Valence Stabilizer #28: Examples of beta-hydroxy thiocarboxylic acids, bis(beta-hydroxy thiocarboxylic acids), poly(beta-hydroxy thiocarboxylic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methyl 3-hydroxythiobutanoate; ethyl 3-hydroxythiobutanoate; phenyl 3-hydroxythiobutanoate; cyclohexyl 3-hydroxythiobutanoate; norbornyl 3-hydroxythiobutanoate; methyl beta-hydroxythiocinnamate; ethyl beta-hydroxythiocinnamate; phenyl beta-hydroxythiocinnamate; methyl o-hydroxythiobenzoate; ethyl o-hydroxythiobenzoate; phenyl o-hydroxythiobenzoate; cyclohexyl o-hydroxythiobenzoate; and norbornyl o-hydroxythiobenzoate.

S—O Valence Stabilizer #29: Examples of beta-mercapto carboxamides, bis(beta-mercapto carboxamides), poly(beta-mercapto carboxamides), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N-methyl 3-mercaptobutanamide; N-ethyl 3-mercaptobutanamide; N-phenyl 3-mercaptobutanamide; N-cyclohexyl 3-mercaptobutanamide; N-norbornyl 3-mercaptobutanamide; N-methyl o-mercaptobenzamide; N-ethyl o-mercaptobenzamide; N-phenyl o-mercaptobenzamide; N-cyclohexyl o-mercaptobenzamide; and N-norbornyl o-mercaptobenzamide.

S—O Valence Stabilizer #30: Examples of S-alkylthiocarboxylic Acids, S-arylthiocarboxylic Acids, and S,S-thiobiscarboxylic Acids (S—O Bidentates and S—O Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: (methylthio)acetic acid; (methylthio)benzoic acid; (methylthio)nicotinic acid; (methylthio)napthoic acid; (phenylthio)acetic acid; (phenylthio)benzoic acid; (phenylthio)naphthoic acid; (norbornylthio)acetic acid; (norbornylthio)benzoic acid; (norbornylthio)napthoic acid; thiobisacetic acid; thiobisbenzoic acid; and thiobisnapthoic acid.

S—O Valence Stabilizer #31: Examples of S-alkyldisulfidocarboxylic acids, S-aryldisulfidocarboxylic acids, and S,S′-disulfidobiscarboxylic acids (S—O Bidentates and S—O Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: (methyldisulfido)acetic acid; (methyldisulfido)benzoic acid; (methyldisulfido)nicotinic acid; (methyldisulfido)napthoic acid; (phenyldisulfido)acetic acid; (phenyldisulfido)benzoic acid; (phenyldisulfido)naphthoic acid; (norbornyldisulfido)acetic acid; (norbornyldisulfido)benzoic acid; (norbornyldisulfido)napthoic acid; S,S′-disulfidobisacetic acid; S,S′-disulfidobisbenzoic acid; and S,S′-disulfidobisnapthoic acid.

S—O Valence Stabilizer #32: Examples of monothiomonocarboxylic acids, dithiodicarboxylic acids, bis(monothiomonocarboxylic acids), bis(dithiodicarboxylic acids), poly(monothiomonocarboxylic acids), poly(dithiodicarboxylic acids), and derivatives thereof (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thioacetic acid; thiopropionic acid; thiobenzoic acid; thiophenylacetic acid; thiocyclohexanoic acid; thiofuroic acid; thionaphthoic acid; phenyl thioacetate; phenyl thiopropionate; phenyl thiobenzoate; phenyl thiocyclohexanoate; phenyl thiofuroate; phenyl thionaphthoate; dithiooxalic acid (dto); monothiooxalic acid (mtox); dithiomalonic acid; dithiosuccinic acid; diphenyl dithiooxalate; diphenyl dithiomalonate; and diphenyl dithiosuccinate.

S—O Valence Stabilizer #33: Examples of monothiocarbonates and bis(monothiocarbonates) (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: S,O-diethyldithiocarbonate; S,O-diisopropyldithiocarbonate; S,O-diphenyldithiocarbonate; S,O-dibenzyldithiocarbon ate; S,O-dicyclohexyldithiocarbonate; and S,O-dinorbornyldithiocarbonate.

S—O Valence Stabilizer #34: Examples of monothiocarbazates (monothiocarbazides), bis(monothiocarbazates), and poly(monothiocarbazates) (S—O Bidentates, S—O Tridentates, and S—O Tetradentates; or possibly N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: N,N′-dimethylmonothiocarbazate; N,N′-di(trifluoromethyl)monothiocarbazate; N,N′-diethylmonothiocarbazate; N,N′-diphenylmonothiocarbazate; N,N′-dibenzylmonothiocarbazate; N,N′-di(pentafluorophenyl)monothiocarbazate; N,N′-dicyclohexylmonothiocarbazate; and N,N′-dinorbornylmonothiocarbazate.

S—O Valence Stabilizer #35: Examples of mercapto alcohols and silylmercaptoalcohols, bis(mercapto alcohols and silylmercaptoalcohols), and poly(mercapto alcohols and silylmercaptoalcohols) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-mercaptoethanol (mel); 3-mercaptopropanol (mpl); 2-mercaptophenol; 2-mercaptocyclohexanol; 3-mercapto-2-norborneol; 2-mercaptopyridine]-oxide; 1,4-thioxane; thiodialkanols; 2-(trimethoxysilyl)-1-ethanethiol (tmset); 3-(trimethoxysilyl)-1-propanethiol (tmspt); o-hydroxythiophenols; o-(O-hydroxyalkyl(aryl))thiophenols; and o-(S-thioalkyl(aryl))phenols.

S—O Valence Stabilizer #36: Examples of monothiocarbimates, bis(monothiocarbimates), and poly(monothiocarbimates) (S—O Bidentates, S—O Tridentates, and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: methylmonothiocarbimate; trifluoromethylmonothiocarbimate; ethylmonothiocarbimate; propylmonothiocarbimate; isopropylmonothiocarbimate; butylmonothiocarbimate; tertbutylmonothiocarbimate; cyanomonothiocarbimate; cyanamidomonothiocarbimate; azidomonothiocarbimate; phenylmonothiocarbimate; pentafluorophenylmonothiocarbimate; benzylmonothiocarbimate; naphthylmonothiocarbimate; cyclohexylmonothiocarbimate; norbornylmonothiocarbimate; and adamantylmonothiocarbimate. [Note: Carbimates tend to stabilize lower oxidation states in metal ions.]

S—O Valence Stabilizer #37: Examples of alkyl- and aryl-monothioborates and bis(monothioborates) (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: O,O′-diethyl monothioborate; O,O′-diisopropyl monothioborate; O,O′-diphenyl monothioborate; O,O′-dibenzyl monothioborate; O,O′-dicyclohexyl monothioborate; and O,O′-dinorbornyl monothioborate.

S—O Valence Stabilizer #38: Examples of alkyl- and aryl-monothioboronates and bis(monothioboronates) (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diethyl monothioboronate; diisopropyl monothioboronate; diphenyl monothioboronate; dibenzyl monothioboronate; dicyclohexyl monothioboronate; and dinorbornyl monothioboronate. [Note: boronates tend to stabilize lower oxidation states in metal ions.]

S—O Valence Stabilizer #39: Examples of monothioarsonic acids (arsonothioic acids), bis(monothioarsonic acids), poly(monothioarsonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: monothioarsonic acid, O-phenylmonothioarsonic acid, O-benzylmonothioarsonic acid, O-cyclohexylmonothioarsonic acid, O-norbornylmonothioarsonic acid, O,O-diphenylmonothioarsonic acid, O,O-dibenzylmonothioarsonic acid, O,O-dicyclohexylmonothioarsonic acid, and O,O-dinorbornylmonothioarsonic acid.

S—O Valence Stabilizer #40: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional oxygen atom binding site not in a ring (S—O Bidentates, S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-thiopheneethanol (2-(2-thienyl)ethanol); 2-propionylthiophene (1-(2-thienyl)-1-propanone); N,N′-thiobisphthalimide; 1,1′-thiocarbonyldi-2-pyridone; 2-thiopheneacetic acid; 2-thiophenecarboxaldehyde; 2-thiophenecarboxamide; 2-thiophenecarboxylic acid; 2,5-thiophenedicarboxaldehyde; 2,5-thiophenedicarboxylic acid; 2-thiophenemethanol; 2-thiophenone; thiotetronic acid; alkyl(aryl) 2-thienyl ketones; dithienyl ketone; 1,3-dithiane-2-carboxylic acid; and 1,3-dithiolane-2-carboxylic acid.

S—O Valence Stabilizer #41: Examples of heterocyclic rings containing one or two oxygen atoms and having at least one-additional sulfur atom binding site not in a ring (S—O Bidentates, S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-furanethanethiol (2-(2-furyl)thanethiol); 1-(2-furyl)-1-propanethione); 2-furanthioacetic acid; 2-furanthiocarboxaldehyde; 2-furanthiocarboxamide; 2-furanthiocarboxylic acid; 2,5-furandithiocarboxaldehyde; 2,5-furandithiocarboxylic acid; 2-furanmethanethiol; 2-furanthione; furfuryl disulfide; furfuryl mercaptan; furfuryl sulfide; and furfuryl methyl disulfide.

S—O Valence Stabilizer #42: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional oxygen atom binding site in a separate ring (S—O Bidentates, S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-furyl)thiophene; 2,5-(2-furyl)thiophene; 2-(2-furyl)thiopyran; and 2,5-(2-furyl)thiopyran.

S—O Valence Stabilizer #43: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol, mercapto, or thiocarbonyl groups) or oxygen (hydroxy, carboxy, or carbonyl groups) and are not contained in component heterocyclic rings (S—O Bidentates, S—O Tridentates, S—O Tetradentates, and S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiaoxacyclobutane ([4]aneOS); thiaoxacyclopentane ([5]aneOS); thiaoxacyclohexane ([6]aneOS); thiaoxacycloheptane ([7]aneOS); thiaoxacyclooctane ([8]aneOS); thiaoxacyclobutene ([4]eneOS); thiaoxacyclopentene ([5]eneOS); thiaoxacyclohexene ([6]eneOS); thiaoxacycloheptene ([7]eneOS); thiaoxacyclooctene ([8]eneOS); dithiaoxacyclohexane ([6]aneOS₂); dithiaoxacycloheptane ([7]aneOS₂); dithiaoxacyclooctane ([8]aneOS₂); dithiaoxacyclononane ([9]aneOS₂); dithiaoxacyclodecane ([10]aneOS₂); dithiaoxacycloundecane ([1]aneOS₂); dithiaoxacyclododecane ([12]aneOS₂); dithiaoxacyclohexene ([6]eneOS₂); dithiaoxacycloheptene ([7]eneOS₂); dithiaoxacyclooctene ([8]encOS₂); dithiaoxacyclononene ([9]eneOS₂); dithiaoxacyclodecene ([10]eneOS₂); dithiaoxacycloundecene ([11]eneOS₂); dithiaoxacyclododecene ([12]eneOS₂); dithiadioxacyclooctane ([8]aneO₂S₂); dithiadioxacyclononane ([9]aneO₂S₂); dithiadioxacyclodecane ([10]aneO₂S₂); dithiadioxacycloundecane ([11]aneO₂S₂); dithiadioxacyclododecane ([12]aneO₂S₂); dithiadioxacyclotridecane ([13]aneO₂S₂); dithiadioxacyclotetradecane ([14]aneO₂S₂); dithiadioxacyclopentadecane ([15]aneO₂S₂); dithiadioxacyclohexadecane ([16]aneO₂S₂); dithiadioxacycloheptadecane ([17]aneO₂S₂); dithiadioxacyclooctadecane ([18]aneO₂S₂); dithiadioxacyclononadecane ([19]aneO₂S₂); dithiadioxacycloeicosane ([20]aneO₂S₂); dithiadioxacyclooctadiene ([8]dieneO₂S₂); dithiadioxacyclononadiene ([9]dieneO₂S₂); dithiadioxacyclodecadiene ([10]dieneO₂S₂); dithiadioxacycloundecadiene ([11]dieneO₂S₂); dithiadioxacyclododecadiene ([12]dieneO₂S₂); dithiadioxacyclotridecadiene ([13]dieneO₂S₂); dithiadioxacyclotetradecadiene ([14]dieneO₂S₂); dithiadioxacyclopentadecadiene ([15]dieneO₂S₂); dithiadioxacyclohexadecadiene ([16]dieneO₂S₂); dithiadioxacycloheptadecadiene ([17]dieneO₂S₂); dithiadioxacyclooctadecadiene ([18]dieneO₂S₂); dithiadioxacyclononadecadiene ([19]dieneO₂S₂); and dithiadioxacycloeicosadiene ([20]dieneO₂S₂).

S—O Valence Stabilizer #44: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or oxygen and are contained in component heterocyclic rings (S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: difurandithiophenes; difurantrithiophenes; trifurantritbiophenes; and tetrafurantetratbiophenes.

S—O Valence Stabilizer #45: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or oxygen and are contained in a combination of heterocyclic rings and thiol, mercapto, thiocarbonyl, hydroxy, carboxy, and carbonyl groups (S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dithiadifurandithiophenes; tetrathiadifurandithiophenes; trithiatrifurantrithiophenes; trithiatrifurantrithiophenes; tetrathiatetrafurantetrathiophenes; and octathiatetrafurantetrathiophenes.

S—O Valence Stabilizer #46: Examples of sulfoxides that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dimethylsulfoxide (DMSO); diethylsulfoxide; diphenylsulfoxide; and tetrahydrothiophene oxide.

S—O Valence Stabilizer #47: Examples of sulfones that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dimethyl sulfone; diethyl sulfone; and diphenyl sulfone.

S—O Valence Stabilizer #48: Examples of sulfur dioxide ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: sulfur dioxide (—SO₂) ligands. [Note: Sulfur dioxide is a reducing agent, and complexed metal ions therefore tend to prefer lower oxidation states.]

N—P Valence Stabilizer #1: Examples of aminoaryl phosphines and iminoaryl phosphines (N—P Bidentates, N—P Tridentates, and N—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tri(2-aminophenyl)phosphine; tri(2-aminophenyl)phosphine oxide; and tri(2-aminopbenyl)phosphine sulfide.

N—P Valence Stabilizer #2: Examples of heterocyclic rings containing one, two, three, or four nitrogen atoms and having at least one additional phosphorus atom binding site not in a ring (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tri(2-imidazolyl)phosphine; tri(2-pyrrolyl)phosphine; tri(2-pyridyl)phosphine; tri(2-imidazolyl)phosphine oxide; tri(2-pyrrolyl)phosphine oxide; tri(2-pyridyl)phosphine oxide; tri(2-imidazolyl)phosphine sulfide; tri(2-pyrrolyl)phosphine sulfide; and tri(2-pyridyl)phosphine sulfide.

N—P Valence Stabilizer #3: Examples of heterocyclic rings containing one, two, or three phosphorus atoms and having at least one additional nitrogen atom binding site not in a ring (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-aminophosphole; 2,5-diaminophosphole; 2-(aminomethyl)phosphole; 2,5-di(aminomethyl)phosphole; 2-aminophosphorin; 2,6-diaminophosphorin; 2-(aminomethyl)phosphorin; 2,6-di(aminomethyl)phosphorin; triaminocyclotriphosphazenes; and hexaminocyclotriphosphazenes.

N—P Valence Stabilizer #4: Examples of heterocyclic rings containing one, two, three, or four nitrogen atoms and having at least one additional phosphorus atom binding site in a separate ring (N—P Bidentates, N—P Tridentates, N—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-pyrrolyl)phosphole; 2,5-di(2-pyrrolyl)phosphole; 2-(2-pyridyl)phosphorin; and 2,6-(2-pyridyl)phosphorin.

N—P Valence Stabilizer #5: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or phosphorus and are not contained in component heterocyclic rings (N—P Bidentates, N—P Tridentates, N—P Tetradentates, and N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclobiphosphazenes; cyclotriphosphazenes; cyclotetraphosphazenes; cyclopentaphosphazenes; cyclohexaphosphazenes; diphosphatetraazacyclooctatetraenes; diphospha-s-triazines; and phospha-s-triazines.

N—P Valence Stabilizer #6: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or phosphorus and are contained in component heterocyclic rings (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphospholedipyrroles; diphosphorindipyridines; triphospholetripyrroles; triphosphorintripyridines; tetraphospholetetrapyrroles; and tetraphosphorintetrapyridines.

N—P V alence Stabilizer #7: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or phosphorus and are contained in a combination of heterocyclic rings and amine, imine, and phosphine groups (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: azaphosphatetraphyrins; diazadiphosphatetraphyrins; azaphosphahexaphyrins; diazadiphosphahexaphyrins; triazatriphosphahexaphyrins; and apholate.

S—P Valence Stabilizer #1: Examples of thioaryl phosphines (S—P Bidentates, S—P Tridentates, S—P Tetradentates, and S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tri(2-mercaptophenyl)phosphine; tri(2-mercaptophenyl)phosphine oxide; and tri(2-inercaptophenyl)phosphine sulfide.

S—P Valence Stabilizer #2: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional phosphorus atom binding site not in a ring (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tri(2-thiophene)phosphine; tri(2-thiopyran)phosphine; tri(2-thiophene)phosphine oxide; tri(2-thiopyran)phosphine oxide; tri(2-thiophene)phosphine sulfide; and tri(2-thiopyran)phosphine sulfide.

S—P Valence Stabilizer #3: Examples of heterocyclic rings containing one, two, or three phosphorus atoms and having at least one additional sulfur atom binding site not in a ring (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-mercaptophosphole; 2,5-dimercaptophosphole; 2-(mercaptomethyl)phosphole; 2,5-di(mercaptomethyl)phosphole; 2-mercaptophosphorin; 2,6-dimercaptophosphorin; 2-(mercaptomethyl)phosphorin; and 2,6-di(mercaptomethyl)phosphorin.

S—P Valence Stabilizer #4: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional phosphorus atom binding site in a separate ring (S—P Bidentates, S—P Tridentates, S—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-thienyl)phosphole; 2,5-di(2-thienyl)phosphole; 2-(2-thienyl)phosphorin; and 2,6-(2-thienyl)phosphorin.

S—P Valence Stabilizer #5: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol, mercapto, or thiocarbonyl groups) or phosphorus and are not contained in component heterocyclic rings (S—P Bidentates, S—P Tridentates, S—P Tetradentates, and S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphathiacyclobutane ([4]anePS); phosphathiacyclopentane ([5]anePS); phosphathiacyclohexane ([6]anePS); phosphathiacycloheptane ([7]anePS); phosphathiacyclooctane ([8]anePS); diphospbathiacyclohexane ([6]aneSP₂); diphosphathiacycloheptane ([7]aneSP₂); diphosphathiacyclooctane ([8]aneSP₂); diphosphathiacyclononane ([9]aneSP₂); diphosphathiacyclodecane ([10]aneSP₂); diphosphathiacycloundecane ([11]aneSP₂); diphosphathiacyclododecane ([12]aneSP₂); diphosphadithiacyclooctane ([8]aneS₂P₂); diphosphadithiacyclononane ([9]aneS₂P₂); diphosphadithiacyclodecane ([10] aneS₂P₂); diphospbadithiacycloundecane ([11]aneS₂P₂); diphosphadithiacyclododecane ([12]aneS₂P₂); diphosphadithiacyclotridecane ([13]aneS₂P₂); diphosphadithiacyclotetradecane ([14]aneS₂P₂); diphosphadithiacyclopentadecane ([15]aneS₂P₂); diphosphadithiacyclohexadecane ([16]aneS₂P₂); diphosphadithiacycloheptadecane ([17]aneS₂P₂); diphosphadithiacyclooctadecane ([18]aneS₂P₂); diphosphadithiacyclononadecane ([19]aneS₂P₂); diphosphadithiacycloeicosane ([20]aneS₂P₂).

S—P Valence Stabilizer #6: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or phosphorus and are contained in component heterocyclic rings (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphospholedithiophenes; diphosphorindithiopyrans; triphospholetrithiophenes; triphosphorintrithiopyrans; tetraphospholetetrathiophenes; and tetraphosphorintetrathiopyrans.

S—P Valence Stabilizer #7: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or phosphorus and are contained in a combination of heterocyclic rings and thiol, mercapto, thiocarbonyl, and phosphine groups (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: thiaphosphatetraphyrins; dithiadiphosphatetraphyrins; thiaphosphahexaphyrins; dithiadiphosphahexaphyrins; and trithiatriphosphahexaphyrins.

P—O Valence Stabilizer #1: Examples of hydroxyaryl phosphines (P—O Bidentates, P—O Tridentates, P—O Tetradentates, and P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tri(2-hydroxyphenyl)phosphine; tri(2-hydroxyphenyl)phosphine oxide; and tri(2-hydroxyphenyl)phosphine sulfide.

P—O Valence Stabilizer #2: Examples of heterocyclic rings containing one or two oxygen atoms and having at least one additional phosphorus atom binding site not in a ring (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tri(2-furan)phosphine; tri(2-pyran)phosphine; tri(2-furan)phosphine oxide; tri(2-pyran)phosphine oxide; tri(2-furan)phosphine sulfide; and tri(2-pyran)phosphine sulfide.

P—O Valence Stabilizer #3: Examples of heterocyclic rings containing one, two, or three phosphorus atoms and having at least one additional oxygen atom binding site not in a ring (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-hydroxyphosphole; 2,5-dihydroxyphosphole; 2-(hydroxymethyl)phosphole; 2,5-di(hydroxymethyl)phosphole; 2-hydroxyphosphorin; 2,6-dihydroxyphosphorin; 2-(hydroxymethyl)phosphorin; and 2,6-di(hydroxymethyl)phosphorin.

P—O Valence Stabilizer #4: Examples of heterocyclic rings containing one or two oxygen atoms and having at least one additional phosphorus atom binding site in a separate ring (P—O Bidentates, P—O Tridentates, P—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(2-furyl)phosphole; 2,5-di(2-furyl)phosphole; 2-(2-furyl)phosphorin; and 2,6-(2-furyl)phosphorin.

P—O Valence Stabilizer #5: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually hydroxy, carboxy, or carbonyl groups) or phosphorus and are not contained in component heterocyclic rings (P—O Bidentates, P—O Tridentates, P—O Tetradentates, and P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: phosphaoxacyclobutane ([4]anePO); phosphaoxacyclopentane ([5]anePO); phosphaoxacyclohexane ([6]anePO); phosphaoxacycloheptane ([7]anePO); phosphaoxacyclooctane ([8]anePO); diphosphaoxacyclohexane ([6]aneOP₂); diphosphaoxacycloheptane ([7]aneOP₂); diphosphaoxacyclooctane ([8]aneOP₂); diphosphaoxacyclononane ([9]aneOP₂); diphosphaoxacyclodecane ([10]aneOP₂); diphosphaoxacycloundecane ([11]aneOP₂); diphosphaoxacyclododecane ([12]aneOP₂); diphosphadioxacyclooctane ([8]aneO₂P₂); diphosphadioxacyclononane ([9]aneO₂P₂); diphosphadioxacyclodecane ([10]aneO₂P₂); diphosphadioxacycloundecane ([1]aneO₂P₂); diphosphadioxacyclododecane ([12]aneO₂P₂); diphosphadioxacyclotridecane ([13]aneO₂P₂); diphosphadioxacyclotetradecane ([14]aneO₂P₂); diphosphadioxacyclopentadecane ([15]aneO₂P₂); diphosphadioxacyclohexadecane ([16]aneO₂P₂); diphosphadioxacycloheptadecane ([17]aneO₂P₂); diphosphadioxacyclooctadecane ([18]aneO₂P₂); diphosphadioxacyclononadecane ([19]aneO₂P₂); diphosphadioxacycloeicosane ([20]aneO₂P₂); and dioxaphospholane.

P—O Valence Stabilizer #6: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen or phosphorus and are contained in component heterocyclic rings (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diphospholedifurans; diphosphorindipyrans; triphospholetrifurans; triphosphorintripyrans; tetraphospholetetrafurans; and tetraphosphorintetrapyrans.

P—O Valence Stabilizer #7: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen or phosphorus and are contained in a combination of heterocyclic rings and hydroxy, carboxy, caibonyl, and phosphine groups (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: oxaphosphatetraphyrins; dioxadiphosphatetraphyrins; oxaphosphahexaphyrins; dioxadiphosphahexaphyrins; and trioxatriphosphahexaphyrins.

As Valence Stabilizer #1: Examples of monoarsines (As Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: arsine, triphenylarsine, ticyclohexylarsine, methyldiphenylarsine, ethyldiphenylarsine, arsinonorbornane, and arsinoadamantane.

As Valence Stabilizer #2: Examples of diarsines (As Monodentates or As—As Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: bis(diphenylarsino)methane, bis(diphenylarsino)ethane, bis(diphenylarsino)propane, bis(diphenylarsino)butane, bis(diphenylarsino)pentane, 1,2-diarsinobenzene, cyclohexane-1,2-diarsine, 1,2-bis(phenylbutylarsino)ethane, o-phenylenebis(methylphenylarsine) and o-phenylenebis(dimethylarsine) (diars). (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

As Valence Stabilizer #3: Examples of triarsines (As—As Bidentates, or As—As Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,1,5,9,9-pentaphenyl-1,5,9-triarsanonane, 3-methyl-3-(As,As-dimethyl)arsinomethyl-1,1,5,5-tetraphenyl-1,5-diarsapentane, As,As-[o-(As-dimethyl)arsinodiphenyl]-(As-phenyl)arsine, As,As-[o-(As-diphenyl)arsinodiphenyl]-(As-phenyl)arsine, hexahydro-2,4,6-trimethyl-1,3,5-triarsinazine. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

As Valence Stabilizer #4: Examples of tetraarsines (As—As Bidentates, As—As Tridentates, or As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 3,3-(As-diphenyl)arsinomethyl-1,1,5,5-tetraphenyl-1,5-diarsapentane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

As Valence Stabilizer #5: Examples of pentaarsines (As—As Bidentates, As—As Tridentates, or As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 4-[2-(As-diphenyl)arsinoethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraarsadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

As Valence Stabilizer #6: Examples of hexaarsines (As—As Bidentates, As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: o-phenylenebis[di-3-(As-diphenyl)arsinopropylarsine]. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)

As Valence Stabilizer #7: Examples of 5-membered heterocyclic rings containing one arsenic atom (As Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: arsole, azarsole, diazarsole, benzarsole, benzazarsole, dibenzarsole, naphtharsole, naphthazarsole.

As Valence Stabilizer #8: Examples of 6-membered heterocyclic rings containing one arsenic atom (As Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: arsenin, azarsenin, diazarsenin, benzarsenin, benzazarsenin, dibenzarsenin, naphtharsenin, and naphthazarsenin.

As Valence Stabilizer #9: Examples of 5-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site not contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(As-phenylarsino)arsole; 2,5-(As-phenylarsino)arsole; 2-(As-phenylarsino)benzarsole; 7-(As-phenylarsino)benzarsole; and 1,8-(As-phenylarsino)dibenzarsole.

As Valence Stabilizer #10: Examples of 6-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site not contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2-(As-phenylarsino)arsenin; 2,5-(As-phenylarsino)arsenin; 2-(As-phenylarsino)benzarsenin; 7-(As-phenylarsino)benzarsenin; and 1,9-(As-phenylarsino)dibenzarsenin.

As Valence Stabilizer #11: Examples of 5-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-biarsole; 2,2′,2″-triarsole; and 2,2′-bibenzarsole.

As Valence Stabilizer #12: Examples of 6-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-biarsenin; 2,2′,2″-triarsenin; 2,2′,2″,2′″-tetraarsenin; 2,2′-bibenzarsenin; and 8,8′-bibenzarsenin.

As Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: As,As-diphenyldiarsacyclobutane ([4]aneAs₂); As,As-diphenyldiarsacyclopentane ([5]aneAs₂); As,As-diphenyldiarsacyclohexane ([6]aneAs₂); As,As-diphenyldiarsacycloheptane ([7]aneAs₂); As,As-diphenyldiarsacyclooctane ([8]aneAs₂); As,As-diphenyldiarsacyclobutene ([4]eneAs₂); As,As-diphenyldiarsacyclopentene ([5]eneAs₂); As,As-diphenyldiarsacyclohexene ([6]eneAs₂); As,As-diphenyldiarsacycloheptene ([7]eneAs₂); and As,As-diphenyldiarsacyclooctene ([8]eneAs₂).

As Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: As,As,As-triphenyltriarsacyclohexane ([6]aneAs₃); As,As,As-triphenyltriarsacycloheptane ([7]aneAs₃); As,As,As-triphenyltriarsacyclooctane ([8]aneAs₃); As,As,As-triphenyltriarsacyclononane ([9]aneAs₃); As,As,As-triphenyltriarsacyclodecane ([10]aneAs₃); As,As,As-triphenyltriarsacycloundecane ([11]aneAs₃); As,As,As-triphenyltriarsacyclododecane ([12]aneAs₃); As,As,As-triphenyltriarsacyclohexatriene ([6]trieneAs₃); As,As,As-triphenyltriarsacycloheptatriene ([7]trieneAs₃); As,As,As-triphenyltriarsacyclooctatriene ([8]trieneAs₃); As,As,As-triphenyltriarsacyclononatriene ([9]trieneAs₃); As,As,As-triphenyltriarsacyclodecatriene ([10]trieneAs₃); As,As,As-triphenyltriarsacycloundecatriene ([11]trieneAs₃); and As,As,As-triphenyltriarsacyclododecatriene ([12]trieneAs₃).

As Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: As,As,As,As-tetraphenyltetraarsacyclooctane ([8]aneAs₄); As,As,As,As-tetraphenyltetraarsacyclononane ([9]aneAs₄); As,As,As,As-tetraphenyltetraarsacyclodecane ([10]aneAs₄); As,As,As,As-tetraphenyltetraarsacycloundecane ([11]aneAs₄); As,As,As,As-tetraphenyltetraarsacyclododecane ([12]aneAs₄); As,As,As,As-tetraphenyltetraarsacyclotridecane ([13]aneAs₄); As,As,As,As-tetraphenyltetraarsacyclotetradecane ([14]aneAs₄); As,As,As,As-tetraphenyltetraarsacyclopentadecane ([15]aneAs₄); As,As,As,As-tetraphenyltetraarsacyclohexadecane ([16]aneAs₄); As,As,As,As,As-etraphenyltetraarsacycloheptadecane ([17]aneAs₄); As,As,As,As-etraphenyltetraarsacyclooctadecane ([18]aneAs₄); As,As,As,As-etraphenyltetraarsacyclononadecane ([19]aneAs₄); and As,As,As,As-tetraphenyltetraarsacycloeicosane ([20]aneAs₄).

As Valence Stabilizer #13d: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: As,As,As,As,As,As-hexaphenylhexaarsacyclododecane ([12]aneAs₆); As—As,As,As,As,As-hexaphenylhexaarsacyclotridecane ([13]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacyclotetradecane ([14]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacyclopentadecane ([15]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacyclohexadecane ([16]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacycloheptadecane ([17]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacyclooctadecane ([18]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacyclononadecane ([19]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacycloeicosane ([20]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacycloheneicosane ([21]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacyclodocosane ([22]aneAs₆); As,As,As,As,As,As-hexaphenylhexaarsacyclotricosane ([23]aneAs₆); and As,As,As,As,As,As-hexaphenylhexaarsacyclotetracosane ([24]aneAs₆).

As Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in component 5-membered heterocyclic rings (As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetraarsoles.

As Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in component 5-membered heterocyclic rings (As—As Tetradentates and As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexaarsoles.

As Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in a combination of 5-membered heterocyclic rings and arsine groups (As—As Tridentates, As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diarsatetraarsoles; and tetraarsatetraarsoles.

As Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (As—As Tridentates, As—As Tetradentates, and As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diarsahexaarsoles; and triarsahexaarsoles.

As Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in component 6-membered heterocyclic rings (As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclotetraarsenins.

As Valence Stabilizer #16b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in component 6-membered heterocyclic rings (As—As Tridentates, As—As Tetradentates, and As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclohexaarsenins.

As Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in a combination of 6-membered heterocyclic rings and arsine groups (As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diarsacyclotetraarsenins; and tetraarsacyclotetraarsenins.

As Valence Stabilizer #17b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in a combination of 6-membered heterocyclic rings and arsine groups (As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diarsacyclohexaarsenins; and triarsacyclohexaarsenins.

Se Valence Stabilizer #1: Examples of monoselenoethers (Se Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hydrogen selenide, dimethyl selenide, diethyl selenide, dioctyl selenide, diphenyl selenide, dicyclohexyl selenide, tetramethylene selenide, trimethylene selenide, dimethylene selenide, and selenobicycloheptane.

Se Valence Stabilizer #2: Examples of diselenoethers (Se Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,5-dimethyl-3,6-diselenaoctane; 2,5-diselenahexane; 2,6-diselenaheptane; 3,7-diselenanonane; 3,6-diselenaoctane; 3-butenyl butyl selenoether (bbs); 4-pentenyl butyl selenoether (pbs); 3-butenyl phenyl selenoether (bps); and 4-pentenyl phenyl selenoether (pps).

Se Valence Stabilizer #3: Examples of triselenoethers (Se Bidentates or Se Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,3,5-triselenane; 2,5,8-triselenanonane; 3,6,9-triselenaundecane; and 2,6,10-triselenaundecane.

Se Valence Stabilizer #4: Examples of tetraselenoethers (Se Bidentates, Se Tridentates, or Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,6,10,14-tetraselenapentadecane and 2,5,8,11-tetraselenadodecane.

Se Valence Stabilizer #5a: Examples of 5-membered heterocyclic rings containing one selenium atom (Se Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydroselenophene, selenophene, selenazole, selenapyrroline, selenaphospholene, selenaphosphole, oxaselenole, selenadiazole, selenatriazole, benzodihydroselenophene, benzoselenophene, benzoselenazole, benzoselenaphosphole, dibenzoselenophene, and naphthoselenophene.

Se Valence Stabilizer #5b: Examples of 5-membered heterocyclic rings containing two selenium atoms (Se Monodentates or Se Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diselenole, benzodiselenole, and naphthodiselenole.

Se Valence Stabilizer #6a: Examples of 6-membered heterocyclic rings containing one selenium atom (Se Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydroselenopyran, selenopyran, selenazine, selenadiazine, selenaphosphorin, selenadiphosphorin, oxaselenin, benzoselenopyran, dibenzoselenopyran, and naphthoselenopyran.

Se Valence Stabilizer #6b: Examples of 6-membered heterocyclic rings containing two selenium atoms (Se Monodentates or Se Bidentates)that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dihydrodiselenin, diselenin, benzodiselenin, dibenzodiselenin, and naphthodiselenin.

Se Valence Stabilizer #7: Examples of 5-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site not contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,5-diseleno-2,5-dihydroselenophene; 2,5-bis(selenomethyl)-2,5-dihydroselenophene; 2,5-bis(2-selenophenyl)-2,5-dihydroselenophene; 2,5-diseleno(selenophene); 2,5-bis(selenomethyl)selenophene; 2,5-bis(2-selenophenyl)selenophene; 2,5-diseleno(selenazole); 2,5-bis(selenomethyl)selenazole; 2,5-bis(2-selenophenyl)selenazole; and 2,5-diseleno-1,3,4-selenadiazole [bismuthselenol].

Se Valence Stabilizer #8: Examples of 6-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site not contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,6-diseleno-2,5-dihydroselenopyran; 2,6-bis(selenomethyl)-2,5-dihydroselenopyran; 2,6-bis(2-selenophenyl)-2,5-dihydroselenopyran; 2,6-diseleno(selenopyran); 2,6-bis(selenomethyl)selenopyran; 2,6-bis(2-selenophenyl)selenopyran; 2,6-diseleno(selenazine); 2,6-bis(selenomethyl)selenazine; 2,6-bis(2-selenophenyl)selenazine; 2,6-diseleno-1,3,5-selenadiazine; 2-seleno-1-benzoselenopyran; 8-seleno-1-benzoselenopyran; and 1,9-diselenodibenzoselenopyran.

Se Valence Stabilizer #9: Examples of 5-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-2,5-dihydroselenophene; 2,2′,2″-tri-2,5-dihydroselenophene; 2,2′-biselenophene; 2,2′,2″-triselenophene; 2,2′-biselenazole; 5,5′-biselenazole; 2,2′-bi-1,3,4-selenadiazole; 2,2′-biselenanaphthene; 2,2′-bibenzoselenazole; and 1,1′-bis(dibenzoselenophene).

Se Valence Stabilizer #10: Examples of 6-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 2,2′-bi-2,5-dihydroselenopyran; 2,2′,2″-tri-2,5-dihydroselenopyran; 2,2′-biselenopyran; 2,2′,2″-triselenopyran; 2,2′-bi-1,4-selenazine; 2,2′-bi-1,3,5-selenadiazine; 2,2′-bi-1-benzoselenopyran; and 1,1′-bis(dibenzoselenopyran).

Se Valence Stabilizer #11a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diselenacyclobutane ([4]aneSe₂); diselenacyclopentane ([5]aneSe₂); diselenacyclohexane ([6]aneSe₂); diselenacycloheptane ([7]aneSe₂); diselenacyclooctane ([8]aneSe₂); diselenacyclobutene ([4]eneSe₂); diselenacyclopentene ([5]eneSe₂); diselenacyclohexene ([6]eneSe₂); diselenacycloheptene ([7]eneSe₂); diselenacyclooctene ([8]eneSe₂); diselenacyclobutadiene ([4]dieneSe₂); diselenacyclopentadiene ([5]dieneSe₂); diselenacyclohexadiene ([6]dieneSe₂); diselenacycloheptadiene ([7]dieneSe₂); and diselenacyclooctadiene ([8]dieneSe₂).

Se Valence Stabilizer #11b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: triselenacyclohexane ([6]aneSe₃); triselenacycloheptane ([7]aneSe₃); triselenacyclooctane ([8]aneSe₃); triselenacyclononane ([9]aneSe₃); triselenacyclodecane ([10]aneSe₃); triselenacycloundecane ([11]aneSe₃); triselenacyclododecane ([12]aneSe₃); triselenacyclohexene ([6]eneSe₃); triselenacycloheptene ([7]eneSe3); triselenacyclooctene ([8]eneSe₃); triselenacyclononene ([9]eneSe₃); triselenacyclodecene ([10]eneSe₃); triselenacycloundecene ([11]eneSe₃); triselenacyclododecene ([12]eneSe₃); triselenacyclohexatriene ([6]trieneSe₃); triselenacycloheptatriene ([7]trieneSe₃); triselenacyclooctatriene ([8]trieneSe₃); triselenacyclononatriene ([9]trieneSe₃); triselenacyclodecatriene ([10]trieneSe ₃); triselenacycloundecatriene ([11]trieneSe₃); and triselenacyclododecatriene ([12]trieneSe₃).

Se Valence Stabilizer #11c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetraselenacyclooctane ([8]aneSe₄); tetraselenacyclononane ([9]aneSe₄); tetraselenacyclodecane ([10]aneSe₄); tetraselenacycloundecane ([11]aneSe₄); tetraselenacyclododecane ([12]aneSe₄); tetraselenacyclotridecane ([13]aneSe₄); tetraselenacyclotetradecane ([14]aneSe₄); tetraselenacyclopentadecane ([15]aneSe₄); tetraselenacyclohexadecane ([16]aneSe₄); tetraselenacycloheptadecane ([17]aneSe₄); tetraselenacyclooctadecane ([18]aneSe₄); tetraselenacyclononadecane ([19]aneSe₄); tetraselenacycloeicosane ([20]aneSe₄); tetraselenacyclooctadiene ([8]dieneSe₄); tetraselenacyclononadiene ([9]dieneSe₄); tetraselenacyclodecadiene ([10]dieneSe₄); tetraselenacycloundecadiene ([11]dieneSe₄); tetraselenacyclododecadiene ([12]dieneSe₄); tetraselenacyclotridecadiene ([13]dieneSe₄); tetraselenacyclotetradecadiene ([14]dieneSe₄); tetraselenacyclopentadecadiene ([15]dieneSe₄); tetraselenacyclohexadecadiene ([16]dieneSe₄); tetraselenacycloheptadecadiene ([17]dieneSe₄); tetraselenacyclooctadecadiene ([18]dieneSe₄); tetraselenacyclononadecadiene ([19]dieneSe₄); tetraselenacycloeicosadiene ([20]dieneSe₄); tetraselenacyclooctatetradiene ([8]tetradieneSe₄); tetraselenacyclononatetradiene ([9]tetradieneSe₄); tetraselenacyclodecatetradiene ([10]tetradieneSe₄); and tetraselenacycloundecatetradiene ([11]tetradieneSe₄).

Se Valence Stabilizer #11d: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexaselenacyclododecane ([12]aneSe₆); hexaselenacyclotadecane ([13]aneSe₆); hexaselenacyclotetradecane ([14]aneSe₆); hexaselenacyclopentadecane ([15]aneSe₆); hexaselenacyclohexadecane ([16]aneSe₆); hexaselenacycloheptadecane ([17]aneSe₆); hexaselenacyclooctadecane ([18]aneSe₆); hexaselenacyclononadecane ([19]aneSe₆); hexaselenacycloeicosane ([20]aneSe₆); hexaselenacycloheneicosane ([21]aneSe₆); hexaselenacyclodocosane ([22]aneSe₆); hexaselenacyclotricosane ([23]aneSe₆); hexaselenacyclotetracosane ([24]aneSe₆); hexaselenacyclododecatriene ([12]trieneSe₆); hexaselenacyclotridecatriene ([13]trieneSe₆); hexaselenacyclotetradecatriene ([14]trieneSe₆); hexaselenacyclopentadecatriene ([15]trieneSe₆); hexaselenacyclohexadecatriene ([16]trieneSe₆); hexaselenacycloheptadecatriene ([17]trieneSe₆); and hexaselenacyclooctadecatriene ([18]trieneSe₆).

Se Valence Stabilizer #12a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in component 5-membered heterocyclic rings (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetraselenophenes; tetraselenaphospholes; tetraoxaselenoles; and tetradiselenoles.

Se Valence Stabilizer #12b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in component 5-membered heterocyclic rings (Se—Se Tridentates or Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexaselenophenes; hexaselenaphospholes; hexaoxaselenoles; and hexadiselenoles.

Se Valence Stabilizer #13a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in a combination of 5-membered heterocyclic rings and selenol and selenoether groups (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diselenatetraselenophenes; tetraselenatetraselenophenes; diselenatetradiselenoles; and tetraselenatetradiselenoles.

Se Valence Stabilizer #13b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in a combination of 5-membered heterocyclic rings and selenol or selenoether groups (Se—Se Tridentates or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diselenahexaselenophenes; and triselenahexaselenophenes.

Se Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in component 6-membered heterocyclic rings (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetraselenopyrans; tetraselenaphosphorins; tetraselenadiphosphorins; tetraoxaselenins; and tetradiselenins.

Se Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in component 6-membered heterocyclic rings (Se—Se Tridentates or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexaselenopyrans; hexaselenaphosphorins; hexaselenadiphosphorins; hexaoxaselenins; and hexadiselenins.

Se Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in a combination of 6-membered heterocyclic rings and selenol or selenoether groups (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diselenatetraselenopyrans; tetraselenatetraselenopyrans; diselenatetraselenaphosphorins; tetraselenatetraselenaphospborins; diselenatetraoxaselenins; tetraselenatetraoxaselenins; diselenatetradiselenins; and tetraselenatetradiselenins.

Se Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in a combination of 6-membered heterocyclic rings and selenol or selenoether groups (Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diselenahexaselenopyrans; triselenahexaselenopyrans; diselenahexaselenaphosphorins; triselenahexaselenaphosphorins; diselenahexaoxaselenins; triselenahexaoxaselenins; diselenahexadiselenins; and triselenahexadiselenins.

Se Valence Stabilizer #16: Examples of 1,3-diselenoketones (diseleno-beta-ketonates), 1,3,5-triselenoketones, bis(1,3-diselenoketones), and poly(1,3-diselenoketones) (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: hexafluoropentanediselenone; 1,3-diphenyl-1,3-propanediselenone; selenobenzoylselenopinacolone; diselenocyclohexoylmethane; diphenylpentanetriselenoate; tetramethylnonanetriselenoate; hexafluoroheptanetriselenoate; trifluoroheptanetriselenoate; 1-(2-thienyl)-1,3-butanediselenone, 1-(2-naphthyl)-1,3-butanediselenone, and trifluoroselenoacetylselenocamphor.

Se Valence Stabilizer #17: Examples of 1,1-diselenolates, bis(1,1-diselenolates), and poly(1,1-diselenolates) (Se—Se Bidentates and Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: 1,1-dicyano-2,2-ethylenediselenolate; 1,1-dicarboalkoxy-2,2-ethylenediselenolate; 1,1-di(trifluoromethyl)-2,2-ethylene diselenolate; 1,1-di(pentafluorophenyl)-2,2-ethylene diselenolate; 1-pentamethylene-2,2-ethylene diselenolate; and 1-nitroethylene diselenolate.

Se Valence Stabilizer #18: Examples of diselenocarbamates, bis(diselenocarbamates), and pqly(diselenocarbamates) (including N-hydroxydiselenocarbamates and N-mercaptodiselenocarbamates) (Se—Se Bidentates, Se—Se Tridentates, and Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: dimethyldiselenocarbamate; di(trifluorodimethyl)diselenocarbamate; diethyldiselenocarbamate; dipropyldiselenocarbamate; diisopropyldiselenocarbamate; dibutyldiselenocarbamate; ditertbutyldiselenocarbamate; dicyanamidodiselenocarbamate; azidoselenoformates; diphenyldiselenocarbamate; di(pentafluorophenyl)diselenocarbamate; dibenzyldiselenocarbamate; dinaphthyldiselenocarbamate; dicyclohexyldiselenocarbamate; dinorbornyldiselenocarbamate; diadamantyldiselenocarbamate; pyrrolidinodiselenocarbamate; piperidinodiselenocarbamate; morpholinodiselenocarbamate; thiamorpholinodiselenocarbamate; 3-pyrrolinodiselenocarbamate; pyrrolodiselenocarbamate; oxazolodiselenocarbamate; isoxazolodiselenocarbamate; thiazolodiselenocarbamate; isothiazolodiselenocarbamate; indolodiselenocarbamate; carbazolodiselenocarbamate; pyrazolinodiselenocarbamate; imidazolinodiselenocarbamate; pyrazolodiselenocarbamate; imidazolodiselenocarbamate; indazolodiselenocarbamate; and triazolodiselenocarbamate.

Se Valence Stabilizer #19: Examples of triselenophosphoric acids (phosphorotriselenoic acids), bis(triselenophosphoric acids), poly(triselenophosphoric acids), and derivatives thereof (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: triselenophosphoric acid, O-phenyltriselenophosphoric acid, O-benzyltriselenophosphoric acid, O-cyclohexyltriselenophosphoric acid, O-norbornyltriselenophosphoric acid, O,Se-diphenyltriselenophosphoric acid, O,Se-dibenzyltriselenophosphoric acid, O,Se-dicyclohexyltriselenophosphoric acid, and O,Se-dinorbornyltriselenophosphoric acid.

Se Valence Stabilizer #20: Examples of diselenophosphoric acids (phosphorodiselenoic acids), bis(diselenophosphoric acids), poly(diselenophosphoric acids), and derivatives thereof (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: diselenophosphoric acid, O-phenyldiselenophosphoric acid, O-benzyldiselenophosphoric acid, O-cyclohexyldiselenophospboric acid, O-norbornyldiselenophosphoric acid, O,)-diphenyldiselenophosphoric acid, O,O-dibenzyldiselenophosphoric acid, O,O-dicyclohexyldiselenophosphoric acid, and O,O-dinorbornyldiselenophosphoric acid.

Se Valence Stabilizer #21: Examples of tetraselenophosphoric acids (phosphorotetraselenoic acids), bis(tetraselenophosphoric acids), poly(tetraselenophosphoric acids), and derivatives thereof (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: tetraselenophosphoric acid, Se-phenyltetraselenophosphoric acid, Se-benzyltetraselenophosphoric acid, Se-cyclohexyltetraselenophosphoric acid, Se-norbornyltetraselenophosphoric acid, Se,Se-diphenyltetraselenophosphoric acid, Se,Se-dibenzyltetraselenophosphoric acid, Se,Se-dicyclohexyltetraselenopbosphoric acid, and Se,Se-dinorbornyltetraselenophosphoric acid.

Se Valence Stabilizer #22: Examples of diselenocarbonates, triselenocarbonates, bis(diselenocarbonates), and bis(triselenocarbonates), (Se—Se Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: Se,Se-diethyldiselenocarbonate; Se Se-diisopropyldiselenocarbonate; Se,Se-diphenyldiselenocarbonate; Se,Se-dibenzyldiselenocarbonate; Se,Se-dicyclohexyldiselenocarbonate; Se,Se-dinorbornyldiselenocarbonate; diethyltriselenocarbonate; diisopropyltriselenocarbonate; diphenyltriselenocarbonate; dibenzyltriselenocarbonate; dicyclohexyltriselenocarbonate; and dinorbornyltriselenocarbonate.

Se Valence Stabilizer #23: Examples of selenocyanate ligands (Se monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn include, but are not limited to: selenocyanate (—SeCN).

Se Valence Stabilizer #24: Examples of selenolates (Se monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: selenophenol; and naphthaleneselenol.

Miscellaneous Valence Stabilizer #1: Examples of diene, bicyclicand tricyclic hydrocarbon ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyclopentadiene; azulene; carotene; norbornane; and adamantane.

Miscellaneous Valence Stabilizer #2: Examples of cyanide and related ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: cyanide (—CN); and fulminate (—CNO).

Miscellaneous Valence Stabilizer #3: Examples of carbonyl ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: carbonyl (—CO); and carbon dioxide (CO₂) ligands.

Miscellaneous Valence Stabilizer #4: Examples of halogens that meet the requirements for use as “narrow band” valence stabilizers for Mn ⁺³and/or Mn⁺⁴include, but are not limited to: fluorine; chlorine; bromine; and iodine.

Water-soluble precursors for the organic valence stabilizers are typically used to ensure that sufficient material is available for pigment synthesis. However, in the case of organic valence stabilizers, it is also possible to synthesize the desired MnIII or MnIV/valence stabilizer compounds from organic solvent systems. Therefore, solubility in organic solvents (for the precursors) is also acceptable. Identification of suitable water soluble precursors can be difficult because many of these organics do not form a wide range of water-soluble compounds.

3e) Mixed Inorganic/Organic Valence Stabilizers

Mixing organic and inorganic valence stabilizers in a pigment solution will often result in a pigment with poor corrosion inhibiting properties because of cross interference. Inorganic and organic stabilizers interact with MnIII and/or MnIV in different ways. For example, inorganic valence stabilizers perform their function by forming a shell of octahedrally or square pyramidally coordinated anionic species around a captured MnIII or MnIV ion. The net charge of these inorganic MnIII- or MnIV-stabilizer compounds is therefore always negative. Organic species stabilize by the formation of a hard or soft bond between the bonding atom in the stabilizer (e.g., oxygen, nitrogen, or sulfur) and the MnIII or MnIV ion. The net charge of these compounds is usually positive. If these two very different types of stabilization ligands are combined, then the magnitude of the charge on the stabilized compound can be significantly reduced. The performance of organic or inorganic stabilized corrosion inhibitor compounds has been found to be related to the ability of the compound to form and sustain a thick electrostatic barrier layer. Additionally, a mixed stabilizer will have a poorly developed electrostatic field and a non-optimal packing around the MnIII or MnIV ion, resulting in a compound with less resistance to aqueous attack. Mixed organic/inorganic stabilized MnIII or MnIV pigments can perform more poorly than pigments that have exclusively inorganic or organic valence stabilizers for this reason.

4) Additional Solubility Control Agents

The use of additional solubility control agents is optional. For example, the anions or cations present in the pigment synthesis bath useful for preparation of “sparingly soluble” pigments may be sufficient to form compounds with the desired solubility and saturated pH characteristics. However, pigment synthesis may produce compounds with greater than optimal solubilities, and the use of additional solubility control agents may be desirable. In situations where fine tuning of solubility or saturated pH is desired, cationic species are typical for MnIII- or MnIV-stabilizer combinations when an inorganic valence stabilizer is used, and anionic species are typical for MnIII or MnIV/organic valence stabilizer combinations.

Additional solubility and saturated pH control can be achieved through the use of nontoxic inorganic cations, which include, but are not limited to: H ⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Mg⁺², Ca⁺², Sr⁺², Y⁺³, La⁺³, Ce⁺³, Ce⁺⁴, Nd⁺³, Pr⁺³, Sc⁺³, Sm⁺³, Eu⁺³, EU⁺², Gd⁺³, Tb⁺³, Dy⁺³, Ho⁺³, Er⁺³, Tm⁺³, Yb⁺³, Lu⁺³, Ti⁺⁴, Zr⁺⁴, Ti⁺³, Hf⁺⁴, Nb⁺⁵Ta⁺⁵, Nb⁺⁴, Ta⁺⁴, Mo⁺⁶, W⁺⁶, Mo⁺⁵, W⁺⁵, Mo⁺⁴, W⁺⁴, Mn⁺², Mn⁺³, Mn⁺⁴, Fe⁺², Fe⁺³, Co⁺², Co⁺³, Ru⁺², Ru⁺³, Ru⁺⁴, Rh⁺³, Ir⁺³, Rh⁺², Ir⁺², PD⁺⁴, Pt⁺⁴, Pd⁺², Pt⁺², Cu⁺², Cu⁺², Cu⁺³, Ag⁺, Ag⁺², Ag⁺³, Au⁺, Au², Au⁺³, Zn⁺², Al⁺³, Ga⁺³, Ga⁺, In⁺³, In⁺, Ge⁺⁴, Ge⁺², Sn⁺², Sn⁺⁴, Sb⁺³, Sb⁺⁵, Bi⁺³, and Bi⁺⁵. Any water-soluble compound containings these cations can be used for this purpose. The nitrates, chlorides, bromides, and perchlorates of these cations offer inexpensive water-soluble precursors, although many other water-soluble precursors exist. The use of alkaline ions such as Mg⁺², Ca⁺², and Sr⁺²for solubility control has been demonstrated successfully, with acceptable saturated pH values.

Cationic solubility control may also be achieved through the use of nontoxic organic cations that include, but are not limited to: quaternary ammonium compounds (NR ₄ ⁺, where R can be any combination of alkyl, aromatic, or acyclic organic substituents, such as the methyltriethylammonium ion); organic compounds containings at least one N⁺ site (such as pyridinium or thiazolium cations); organic compounds containing at least one phosphonium site (P⁺, such as the benzyltriphenylphosphonium ion); organic compounds containing at least one stibonium site (Sb⁺, such as the tetraphenylstibonium ion); organic compounds containing at least one oxonium site (O⁺, such as pyrylium cations); organic compounds containing at least one sulfonium site (S⁺, such as the triphenylsulfonium ion); and organic compounds containing at least one iodonium site (I⁺, such as the diphenyliodonium ion).

The quaternary ammonium compounds, organic compounds containing at least one N ⁺ site, and organic compounds containing at least one oxonium site are the most important of these classifications because of the very large number of stable cations that are available. Water-soluble precursors for these organic cations are desirable in order to maximize the amount of material available in the appropriate pigment synthesis solution. Most of these materials are also soluble in organic solvents and hydrocarbons. Fluorides, chlorides, and bromides offer the most water-soluble precursors for these organic cations, although nitrates and perchlorates of those cations with lower molecular weights (e.g., tetramethylammonium) are also acceptable water-soluble precursors. Nitrates and perchlorates of larger (greater molecular weight) organic cations are generally not acceptable as precursors because of their low water solubility.

Toxic inorganic or organic cations can be used as additional solubility control agents although this is less desirable. Examples of toxic inorganic cations that can be used include, but are not limited to: Be ⁺², Ba⁺², V⁺⁵, V⁺⁴, V⁺³, Cr⁺³, Ni⁺², Ni⁺⁴, Os⁺⁴, Cd⁺², Hg⁺¹, Hg⁺², Tl⁺, Tl⁺³, As⁺³, As⁺⁵, Pb⁺², and Pb⁺⁴. Examples of toxic organic cations include, but are not limited to: organic compounds containing at least one arsonium site (an example being the tetraphenylarsonium ion of As⁺) and organic compounds containing at least one selenonium site (an example being the triphenylselenonium ion of Se⁺). Use of these materials for additional solubility control may be necessary in some specific instances where the toxicity of the resulting pigment is of limited importance to the operator. Water-soluble precursors for these toxic cations are typical in order to maximize the amount of available cation for solubility control in aqueous-based synthesis solutions. The organic cations are frequently hydrocarbon-soluble. In general, the nitrates, chlorides, bromides, and perchlorates of these cations offer the highest water solubility.

Additional solubility control can also be achieved by using nontoxic inorganic anions, especially for MnIII or MnIV/organic valence stabilizer combinations. Soluble precursors for these inorganic anions are desirable in order to maximize the amount of material available in the appropriate pigment formation solution. Inorganic examples include, but are not limited to: fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, and heteropolyanions (e.g., heteropolymolybdates or silicomolybdates).

Additional solubility control can also be achieved through the use of an almost unlimited number of nontoxic organic anions (e.g., organics with different carboxylate or acid groups). Examples include, but are not limited to: ferricyanides; ferrocyanides; cyanocobaltates; cyanocuprates; cyanomanganates; cyanates; cyanatoferrates; cyanatocobaltates; cyanatocuprates; cyanatomanganates; thiocyanates; thiocyanatoferrates; thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates; cyanamides; cyanamidoferrates; cyanamidocobaltates; cyanamidocuprates; cyanamidomanganates; nitritoferrates; nitritocobaltates; azides; (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, or tetra(thio)carboxylates [useful representatives including, but not limited to, acetic acid, benzoic acid, succinic acid, fumaric acid, salicylic acid, lactic acid, tartaric acid, antimonyl tartrates, cinnamic acid, adipic acid, phthalic acid, terephthalic acid, citric acid, ascorbic acid, malic acid, malonic acid, oxalic acid, stearic acid, gallic acid, naphthenic acid, camphoric acid, nitrosalicylic acid, aminosalicylic acid, acetylsalicylic acid, sulfosalicylic acid, nitrobenzoic acid, perfluoroC _2-16carboxylic acids, trinitrobenzoic acid, chlorobenzoic acid, anisic acid, iodobenzoic acid, anthranilic acid, mandelic acid, toluic acid, nicotinic acid, isonicotinic acid, pyrazolecarboxylic acid, picrolonic acid, quinaldic acid, diphenic acid, benzoquinaldic acid, quinolinecarboxylic acid, isoquinolinecarboxylic acid, triazinecarboxylic acid, (thio)carbonic acids, (thio)carbamic acids, trimethylhexylic acid, tetrafluorophthalic acid, ethylenediaminetetraacetic acid, toluoylpropionic acid, lactobionic acid, octylthiopropionate, lipoic acid, methylbenzoylpropionic acid, anthracenesuccinic acid, benzothiazolecarboxylic acid, phenylacetic acid, glycolic acid, thioglycolic acid, benzothiazolylthiosuccinic acid, benzothiazolylthiopropionic acid, phenylanthranilic acid, furancarboxylic acid, nitrofuroic acid, phosphonobutanetricarboxylic acid benzothiazolylthiosuccinic acid, N-phosphonomethylglycine, cresoxyacetic acid, aminobutyric acid, alanine, asparagine, cysteine, glutamine, glycine, leucine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, glutamic acid, aspartic acid, arginine, histidine, lysine, trihydroxyglutaric acid, phenoxyacetic acid, hydroxynaphthoic acid, phenylbutyric acid, hydroxyphosphonoacetic acid, tropic acid, aminophenylpropionic acid, dihydrocinnamic acid, hydroxycinnamic acid, cinchomeronic acid, aurintricarboxylic acid, benzotriazolecarboxylic acid, hydroxyphosphonoacetic acid, cyanuric acid, barbituric acid, violuric acid, diphenylvioluric acid, dilituric acid, thiobarbituric acid, cresotic acid, trimethylhexylic acid, nitrilotriacetic acid, N,N′-terephthaloylbis(aminocaproic acid), ethyleneglycolbis(aminoethylether)tetraacetic acid, diethylenetriaminepentaacetic acid, 2-phosphonobutanetricarboxylic acid, N,N′-bis(2-hydroxysuccinyl)ethylenediamine, nicotinic acid, naptalam, nitrobenzoic acid, nonylphenoxyacetic acid, and olsalazine]; (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, or tetra(thio)phenolates [useful representatives including, but not limited to, pyrocatechol, resorcinol, picric acid, styphnic acid, pyrogallol, purpurin, purpurogallin, benzopurpurin, gallein, thiophenol, rhodizonic acid, kojic acid, chromotropic acid, carminic acid, fluorescein, tannic acid, and humic acid]; (thio)phosphonates, di(thio)phosphonates, or tri(thio)phosphonates [useful representatives including, but not limited to, diethylphosphonic acid, diphenylphosphonic acid, nitrophenylphosphonic acid, perfluoroC_2-16phosphonic acids, benzenephosphonic acid, phytic acid, hydroxyethylidenebisphosphonic acid, nitrilotrimethylenephospbonic acid, aminomethylenephosphonic acid, etidronic acid, ethylphosphonic acid, chloroethylphosphonic acid, ethylenediaminotetramethylenephosphonic acid, laurylhydroxydiphosphonic acid, methylaminodimethylenephosphonic acid, alkyl(aryl)diphosphonic acids, N-cetylaininoethanediphosphonic acid, carboxyhydroxymethylphosphonic acid (hpa), oxyethylidenediphosphonic acid, polycaproamidophosphonates, phenylethanetriphosphonic acid, oxidronic acid, and pamidronic acid]; (thio)phosphonamides, di(thio)phosphonamides, or tri(thio)phosphonamides [useful representatives including, but not limited to, phosphoramidic acid, phosphordiamidic acid (diamidophosphonic acid), and phosphoramidothioic acid]; amino(thio)phosphonates, diamino(thio)phosphonates, or triamino(thio)phosphonates; imino(thio)phosphonates or diimino(thio)phosphonates; (thio)sulfonates, di(thio)sulfonates, or tri(thio)sulfonates [useful representatives including, but not limited to, methanesulfonic acid, benzenesulfonic acid, aminobenzenesulfonic acid (sulfanilic acid), nitrobenzenesulfonic acid, phenylsulfonic acid, naphthalenesulfonic acid, nitronaphthalenesulfonic acid, oxinesulfonic acid, alizarinsulfonic acid, benzidinesulfonic acid, flavianic acid, camphorsulfonic acid, diiodophenolsulfonic acid (sozoiodol), 8-hydroxyquinoline-5-sulfonic acid, 7-nitro-8-hydroxyquinoline-5-sulfonic acid; benzotriazolesulfonic acid, bis(trifluoromethyl)benzenesulfonic acid, diiododihydroxybenzophenonesulfonic acid, p-amino-p′-ethoxydiphenylamine-o-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid; 1,2-diaminoanthraquinone-3-sulfonic acid, 1,5-dinitro-2-naphthol-7-sulfonic acid, perfluoroC_2-16sulfonic acids, benzenedisulfonic acid, phenyldisulfonic acid, naphthalenedisulfonic acid, 3,6-naphtholdisulfonic acid, indigodisulfonic acid, benzidinedisulfonic acid, carboxyiodobenzenesulfonic acids; N-benzeneaminomethanesulfonic acid (ams); amido-G-acid; amido-R-acid; naphthalene(di)sulfonic acid (Armstrong's acid); amsonic acid; Badische acid; camphorsulfonic acid; chrysophenine; Cassella's acid; chromotropic acid; Cleve's acid; croceic acid; anthracenesulfonic acid; hydroxyquinolinesulfonic acid; hydrazinobenzenesulfonic acid; indigo cannine; indoxyl; isatinsulfonic acid; indican; lignosulfonic acid; metanil yellow; metanilic acid; naphthoquinonesulfonic acid; Nuclear Fast Red; naphthol(di)sulfonic acid; naphthylamine(di)sulfonic acid; Orange I; orthanilic acid; phenol(di)sulfonic acid; methylenedinapbthalenesulfonic acid; methyl orange; and piperazinediethanesulfonic acid (pipes)]; (thio)sulfonamides, di(thio)sulfonamides, or tri(thio)sulfonamides; amino(thio)sulfonates, diamino(thio)sulfonates, or triamino(thio)sulfonates; imino(thio)sulfonates (including sulfamates) or diimino(thio)sulfonates (including disulfamates) [useful representatives including, but not limited to, methylsulfamic acid and phenylsulfamic acid]; (thio)borates, di(thio)borates, or (thio)boronates [useful representatives including, but not limited to, phenylboric acid and borotartaric acid]; organic silicates; and stibonates [useful representatives including, but not limited to, antimonyl tartrate and benzenestibonic acid]. Soluble precursors for these organic anions are desirable to maximize the amount available in the appropriate pigment synthesis solution. These organic anions are frequently soluble in organic solvents or hydrocarbons in addition to water-based systems.

Finally, toxic inorganic or organic anions can be used as additional solubility control agents, although they are less desirable. Examples of toxic inorganic anions include, but are not limited to: arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions (e.g., Nessler's reagent), thiocyanatomercury anions (e.g., Behren's reagent), chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, and vanadates. Examples of toxic organic anions include cyanides; cyanochromates; cyanonickelates; cyanatochromates; cyanatonickelates; thiocyanatochromates; thiocyanatonickelates; cyanamidochromates; cyanamidonickelates; nitritonickelates; arsonates, diarsonates, or triarsonates [useful representatives being propylarsonic acid, phenylarsonic acid, hydroxyphenylarsonic acid, benzenearsonic acid, methylbenzenearsonic acid, hydroxybenzenearsonic acid, and nitrobenzenearsonic acid]; and organic selenates, diselenates, or triselenates. These materials may be necessary in some specific instances for additional solubility control where toxicity of the final pigment material is of limited importance. Soluble precursors for these organic anions are desirable to maximize the amount available in the appropriate pigment synthesis solution. The alkali or ammonium species of these anions typically offer the greatest water solubility.

Solubility control agents can also be used for “low solubility” and “insoluble” MnII and MnIV pigments for use as lead chromate and/or red lead replacements. However, the choice of solubility control agents is limited due to the chemistry and preparation methods for these pigments. These pigments are typically prepared by calcining, firing, or otherwise heating powder mixtures, so organic solubility control agents are not acceptable because of thermal degradation. In addition, because these calcined or fired manganese-containing mixtures result in complex oxide compounds, there is no need to add anionic solubility control agents. The only solubility control agents suitable for use with the “low solubility” or “insoluble” MnII or MnIV pigments will overwhelmingly be inorganic cations.

Solubility control agents for calcined, fired, or otherwise heated MnIII and/or MnIV-containing pigments include, but are not limited to: Li ⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be⁺², Mg⁺², Ca⁺², Sr⁺², Ba⁺², Y⁺³, La⁺³, Ce⁺³, Ce⁺ ⁴, Ti⁺⁴, Zr⁺⁴, V⁺⁵, Nb⁺⁵, Ta⁺⁵, Mo⁺⁶, W⁺⁶, Cr⁺³, Mn⁺², Fe⁺³, Fe⁺², Co⁺², Co⁺³, Ni⁺², Cu⁺², Ag⁺, Ag⁺², Zn⁺², Al⁺³, In⁺³, Sn⁺⁴, Sb⁺³, Sb⁺⁵, Bi⁺³, and Bi⁺⁵. Table 6 shows example compositions of low solubility or insoluble MnIII or MnIV compounds suitable as pigments that can be produced for many of these solubility control cations. It is interesting to note the similarity between these compositions and those shown in Table I for naturally-occurring MnIII or MnIV minerals, further validating their longterm stability. As the solubility control cation is changed, dramatic differences in solubility can be observed. For example, Mg-containing MnIII or MnIV pigments (i.e., MgM_n ₂O₄) exhibit higher solubilities (i.e., 10⁻⁴moles/liter MnIII or MnIV) whereas Ba-containing MnIII or MnIV pigments (i.e., BaMnO₃) exhibit much lower (i.e., 10⁻⁸or 10⁻⁹moles/liter MnIII or MnIV) solubilities. In this way, even the performance of calcined or fired MnIII or MnIV ceramic powders can be tailored for specific applications. Combinations of these ions can also be used to modify performance.

It has been noted that one of the primary functionalities of lead chromate and especially red lead pigments is the ability to insolubilize corrosive anions (especially sulfate) via the divalent lead ion. Similar functionality can be achieved using proper choice of the solubility control agents described above. For example, barium (Ba ⁺²) is notorious for its ability to insolubilize sulfate ions. Bismuth (Bi⁺³) can produce insoluble chlorides under the proper conditions. Therefore, of the cationic solubility control agents listed above for “low solubility” or “insoluble” MnIII and MnIV pigments, those containing Ba⁺², Bi⁺³, and Bi⁺⁵are typical.

Similarly, compositions containing cations that are themselves corrosive towards structural metals are less desirable. Hence, compositions containing potassium (K ⁺) and especially sodium (Na⁺) are less desirable.

TABLE 6


Representative Examples of Low Solubility or Insoluble MnIII or MnIV Pigments
Suitable For Lead Chromate or Red Lead Replacements

Solubility Control Cation	Example Composition(s)	Comments

None	MnO₂, Mn₃O₄, Mn₂O₃,	No compositional modification of
	MnO(OH), Mn(O,OH)₂	properties
Lithium (Li⁺)	LiMn₂O₄
Magnesium (Mg⁺²)	MgMn₂O₄	Highest solubility of
	MgMnO₃	calcined pigments
		MgMnO₃is unstable
		Solid solutions with
		MgAl₂O₄or MgFe₂O₄also
		possible
Calcium (Ca⁺²)	CaMnO₃, CaMn₂O₄,	CaMnO₃most stable
	Ca₂MnO₄	Solid solutions with Co,
		Fe, Ni, Bi, Ba, Zn, Sr, La,
		Ce, and Y formulas also
		possible
Strontium (Sr⁺²)	SrMnO₃	Solid solutions with Ca,
		Zn, Ba, Bi, La, Ce, and Y
		formulas also possible
Barium (Ba⁺²)	BaMnO₃, BaMn₈O₁₆	Solid solutions with Sr,
		Ca, Zn, Bi, La, Y, and Ce
		formulas also possible
Zinc (Zn⁺²)	ZnMn₂O₄, ZnMn₃O₇	Solid solutions with Co,
		Cu, Ni, Fe, Ca, Sr, Ba, La,
		Ce, Y, and Bi formulas also
		possible
Bismuth (Bi⁺³)	BiMnO₃, BiMn₂O₅	Solid solutions with Ca,
		Sr, Ba, Zn, La, Ce, and Y
		formulas also possible
Lanthanum (La⁺³)	LaMnO₃	Solid solutions with Sr,
		Ca, Zn, Ba, Ce, Bi, and Y
		formulas also possible
Cerium (Ce⁺³)	CeMnO₃	Solid solutions with Sr,
		Ca, Zn, Ba, Bi, La, and Y
		formulas also possible
Yttrium (Y⁺³)	YMnO₃	Solid solutions with Sr,
		Ca, Zn, Ba, Bi, La, and Ce
		formulas also possible
Aluminum (Al⁺³)	AlMn₂O₄	Exhibits higher solubility
		Somewhat unstable
Cobalt (Co⁺²)	CoMn₂O₄, CoMn₃O₇	Solid solutions with Ni,
		Fe, Zn, Cu, and Ca formulas
		also possible
Nickel (Ni⁺²)	NiMn₂O₄, NiMn₃O₇	Solid solutions with Co,
		Fe, Zn, Cu, and Ca formulas
		also possible
Iron (Fe⁺²)	FeMn₂O₄, FeMn₃O₇	Solid solutions with Co,
		Ni, Zn, Cu, and Ca formulas
		also possible
Copper (Cu⁺²)	CuMn₂O₅, CuMn₃O₇	Solid solutions with Zn,
		Co, Fe, Ni formulas also
		possible

5) Valence Stabilizers for “Indicator Pigments”

Some heteropolymetallate valence stabilizers for trivalent or tetravalent manganese pigments have been observed to result in pigments that change color as the MnIII- or MnIV-stabilizer compound was exhausted during corrosion. For example, molybdate-stabilized MnIV pigments are typically moroon in color after being prepared and combined with a suitable binder system. These pigments were observed to gradually change from maroon to royal blue after extended exposure to ASTM B-117 and ASTM G-85 accelerated corrosion testing environments. The rate of color change was gradual with time and scaled with initiation and continued corrosion of the substrate. The color change from maroon to blue is well-documented in the inorganic chemistry literature for heteropolymolybdates. Numerous studies have shown that the color change associated with molybdenum blues is due to reduction of the molybdenum (VI) ion (the valence stabilizer for MnIV in this example), to the more reduced molybdenum (IV) ion. Other manganese-containing compounds can exhibit differences in color with the change in valence of the manganese ion in the pigment compound. Organometallic literature has many examples of manganese compounds where an organic trivalent or tetravalent manganese compound is one color and the divalent compound is a different color.

Color changes in the paint can be used as a metric to determine when the corrosion-inhibiting ability of the pigment has begun to fail. Alternatively, changes in pigment color hue may suggest remaining corrosion-inhibiting service life. The color change behavior is not observed for all MnIII- or MnIV-valence stabilizer combinations. Those compositions that do exhibit a significant color change between fully oxidized and reduced valence states are typical for applications where an indication of the amount of remaining unreacted pigment is desired. This represents an advantage over conventional chromate or plumbate pigments which do not demonstrate a significant color change during reduction.

B) Pigment Synthesis

The manganese compounds of the present invention can be synthesized by many different formation routes, and the synthesis of specific trivalent or tetravalent manganese compounds is often found in the general manganese coordination chemistry literature. The syntheses of several trivalent or tetravalent manganese compounds suitable for use as pigments are outlined in the Examples section of this specification.

The pigments can be synthesized via precipitation routes (including onto inorganic or organic substrates), by firing of constituents, by evaporative routes, etc. In general, “sparingly soluble” MnIII and MnIV pigments are best prepared by precipitation or evaporation routes, whereas “low solubility” or “insoluble” MnIII and MnIV pigments are best prepared by firing of constitutents. Precipitation is a typical synthesis route, for “sparingly soluble” pigments because: a) it is easiest to control, b) it allows inorganic valence stabilizers to polymerize, and c) many organic valence stabilizer precursors are degraded by high temperatures. Precipitation from aqueous (water-based) solutions is typical, because the formed trivalent or tetravalent manganese pigment materials are required to be sparingly soluble in water in order to function adequately as corrosion-inhibitors. For the more soluble pigments (i.e., with solubilities as high as 1×10 ⁰moles/liter of trivalent or tetravalent manganese, for specialized applications), precipitation can be aided by traditional salting-out methodologies, such as adding salt or alcohols to further facilitate precipitation. If desired, precipitation onto or in combination with inert materials such as oxides, hydroxides, silicates, borates, aluminates, phosphates, carbonates, titanates, molybdates, tungstates, oxalates, polymers, etc., can be initiated. An almost infinite variety of colors, hues, tints, solubilities, saturated pHs, decomposition temperatures, melting points, and corrosion-inhibiting action can be produced in pigments based solely on the MnIII or MnIV ions.

Organic solvents can also be used for the synthesis of these pigments, especially for many of the organic valence-stabilized manganese compounds. Conventional organic solvents include, but are not limited to: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, benzyl alcohol, glycerol, ethylene glycol, propylene glycol, cresol, cycldhexanol, butyl carbitol, cellosolve, methyl cellosolve, ethyl lactate, acetone, methyl ethyl ketone (MEK), diethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, acetophenone, diethyl ether, isopropyl ether, furan, tetrahydrofuran (THF), dioxane, tetrahydropyran, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, propylene oxide, acetic acid, propionic acid, butyrolactone, ethylene carbonate, propylene carbonate, benzaldehyde, propyl amine, diethyl amine, ethanolamine, aniline, pyridine, acetonitrile, dimethylformamide (DMF), propionitrile, nitrobenzene, hexane, cyclohexane, benzene, toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, Freon 1113, carbon disulfide, dimethyl sulfoxide (DMSO), and hexamethylphosphoric triamide (HMPT). These solvents can be used in instances where the specific MnIII or MnIV/valence stabilizer is insoluble in that specific solvent and sparingly soluble in water, or in instances where evaporative formation of fine particle sizes is desired.

A typical MnIV compound with-inorganic valence stabilization was prepared as follows:

1) the stabilizer was dissolved in a minimum of water with added acetic acid or sodium acetate to buffer the solution to the proper pH;

2) manganese nitrate was dissolved in a separate buffered water solution;

3) the stabilizer solution was heated to near boiling and the manganese solution added all at once;

4) this stabilizer-manganese solution was heated for 15 to 60 minutes with a potassium acetate buffer to initiate inorganic polymerization of the valence stabilizer in the presence of a persulfate oxidizer to form tetravalent manganese;

5) this solution (mother liquor) was cooled and any precipitate filtered;

6) the mother liquor was separated into five fractions and an additional solubility control agent was added; and

7) each solution from step 6 was ice chilled and precipitates filtered and dried.

Solubility control agents Mg, Ca, Zn, Sr, and Ba were used to obtain a broad spectrum of solubilities with a single MnIV-valence stabilizer combination. Occasionally a precipitate would not form with the addition of a “solubility control agent” or a day of evaporation. This would imply that the target compound was extremely water soluble and unsuited for use as a pigment. Conversely, a precipitate would occasionally form immediately on addition of the last pH buffer or even the oxidizing agent. This would imply that the target MnIV compound was extremely insoluble and unsuited for use as a corrosion inhibiting pigment when incorporating the buffer or oxidizer's cations.

MnIII and MnIV pigments with organic valence stabilizers were synthesized in a similar fashion. Water-soluble organic ligands (i.e., the azo dye examples) allowed the entire synthesis to be performed in aqueous solution. Valence stabilizers of low water solubility (i.e., 8-hydroxyquinoline) were complexed in an isopropanol/water mixture. It was not necessary to carefully control pH of the organic syntheses because polymerization like that needed for the heteropolymetallate inorganic stabilizers was not necessary. Anionic “solubility control agents” such as sulfate, phosphate, molybdate, tungstate, and phosphomolybdate were used for the organic examples to form progressively larger compounds with less solubility.

The color of MnIII or MnIV pigments depends on the specific MnIII or MnIV-valence stabilizer combination. Inorganically valence stabilized MnIII or MnIV compounds ranged from maroon to black. The color of MnIII and MnIV-pigments incorporating organic valence stabilizers often matched the color of the valence stabilizer. This was particularly true of the azo dyes. The colors of the organically stabilized pigments were orange-yellow ranging to green or brown.

Oxidation of divalent manganese to the trivalent or tetravalent oxidation state can be performed prior to, or after, compound formation. If trivalent or tetravalent manganese salts are to be used for synthesis, then additional oxidation may or may not be necessary, depending upon the synthesis conditions. For example, a MnIII or MnIV/valence stabilizer coordination compound could be prepared, or a MnII/valence stabilizer compound could be prepared and subsequently oxidized to a MnIII or MnIV/valence stabilizer compound. Oxidation prior to compound formation is typical, however, to ensure that the stability of the formed compound is maintained.

The stability of compounds using the same valence stabilizer ligand differs significantly because of the difference in size between the MnII, MnIII, and MnIV ions (67 pm versus 61 pm versus 54 pm). This has to do with the size requirements of the coordinating ligand. Therefore, one ligand geometry may result in a very stable MnIII compound, but the same compound containing MnIII or MnIV can, in many instances, exhibit lower stabilities because of the difference in size of the ions. Oxidation to the trivalent or tetravalent state prior to precipitation (or other preparative methodology) ensures that once recovered, the compound is for the most part in a usable form.

Preparation of a divalent manganese compound, with subsequent oxidation treatment (e.g., via steam, gaseous oxygen, concentrated liquid oxidizer, etc.) to convert the compound to a trivalent or tetravalent oxidation state, can degrade the ligand or the entire compound, or can alter substituent groups on that ligand. Trivalent or tetravalent manganese/valence stabilizer complexes having a melting temperature lower than approximately 50° C. can be produced as a low melting solid, or a liquid-phase inhibitor. They can also be combined with inert materials in order to provide a solid material. If combination with inert materials is desired, then the trivalent or tetravalent corrosion inhibiting compound can be absorbed into, or adsorbed onto, the surfaces of the inert particles. The particles can be inorganic (e.g., oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof) or organic (e.g., polymeric) in nature.

If low solubility or insoluble MnIII or MnIV compounds are desired, then calcining, heating, or firing of mixtures of compounds in an oxidizing environment represents the simplest route to formation. Firing temperatures of between about 200 and about 1200° C. typically can be used depending upon the specific composition. MnII, MnIII, MnIV, or even MnVII precursors can be used for this preparation.

Once synthesized, the pigments can then be incorporated into a wide range of binder systems to afford corrosion protection. Examples of organic binder systems that can incorporate MnIII or MnIV corrosion-inhibiting pigments include, but are not limited to: alkyd-type primers, acrylic primers, polyester primers, epoxy primers, conductive primers, organic sol-gels, ketimine coatings, polyvinyl coatings, acrylic thermoplastics, asphaltic and coal tar thermoplastics, polyamide thermoplastics, polyethylene dispersion thermoplastics, fluorocarbon thermoplastics, chlorocarbon thermoplastics, silicone thermosets, polyurethane thermosets, polyester thermosets, epoxy-amine thermosets, epoxy-amide thermosets, epoxy-ester thermosets, epoxy-coal tar thermosets, furane thermosets, phenolic thermosets, butadiene styrene elastomers, chlorinated rubber elastomers, polysulfonated elastomers, neoprene elastomers, sulfur-containing rubbers, or combinations thereof. Examples of inorganic binder systems that can incorporate MnIII or MnIV pigments include, but are not limited to: low temperature enamels, low temperature glass frits, carbonaceous coatings, zeolites, inorganic sol-gels, or combinations thereof.

EXAMPLES

In order that the invention may be more readily understood, reference is made to the following examples, which are intended to illustrate the invention, but not limit the scope thereof [0758]
1) Wash Primer Preparation [0759]
The corrosion inhibiting performance of MnIII and MnIV pigments was evaluated by incorporating them into primer paint formulations. The acid wash primer paint formulation called out in DoD-P-15328 [Primer (Wash), Pretreatment (Formulation No. 117 for Metals)] was used to test the synthesized pigments. The wash primer is composed of a resin, an acid, a corrosion inhibiting pigment, powdered talc, and carbon lampblack. The acid content of this wash primer provides a rigorous initial test of the stability and performance of the pigments. Other, more benign, polymer-based binder and resin systems might not separate the compounds based on their performance as effectively or as rapidly. [0760]
The base solution for the wash primer in this specification was prepared by mixing 88.3 grams of isopropanol, 31.3 grams of n-butanol, and 3.8 grams of deionized water with 14 grams of poly(vinyl butyral) resin (PVB) (Monsanto Butvar B-90™). PVB was used exclusively throughout testing to avoid preparation and compositional complications during analysis of pigment performance. However, the invention is not limited to the use of PVB. [0761]
Acid diluent was prepared by mixing 70 grams of 85% phosphoric acid, 63 grams of deionized water, and 247 grams of isopropanol. Finely-ground pigment powder was measured out and added to 13.74 grams of the base solution for each paint to be tested. A small amount (0.2 g) of powdered talc (magnesium silicate) “filler” was added. Lampblack was not added to these samples. These components were mixed thoroughly by hand and 3.8 g of phosphoric acid diluent added with further mixing. This rough processing allowed direct comparisons of pigment performance to be made without complications due to powder treatments, modifications, and additives. [0762]
For each pigment to be tested, the primer paint was applied onto 10 metal substrates −5 precleaned 7075-T6 and 5 precleaned 2024-T3 aluminum substrates. This is not the conventional paint application procedure for aluminum alloys. Under normal service conditions, aluminum alloys are first subjected to a hexavalent chromium-containing conversion coating prior to primer application. However, the conversion coating was omitted so that the performance of the pigment alone could be evaluated and not the synergistic effects of hexavalent chromium (in the conversion coating) or even of barrier films (in the phosphate or anodized coatings). [0763]
Multiple samples of specific pigment compositions were prepared and tested. Samples treated with zinc and strontium chromate were used as comparison standards. The chromate pigments were prepared identically to those used to test MnIII and MnIV composition variations. [0764]
2) Corrosion Testing [0765]
PVB wash primers containing various pigment formulations were evaluated by exposing them to static salt fog (ASTM B-117) and cyclic Prohesion™ (ASTM G-85.5) accelerated corrosion tests. ASTM B-117 is a traditional corrosion “proof” test that has little relation to a real working environment. This accelerated corrosion test exposes samples to a constant salt-water fog and is a de facto test of solubility for corrosion inhibitors. B-117 does not necessarily test the ability of a corrosion inhibitor to actually inhibit corrosion. This is particularly true of inhibitors and compounds that have not been fully optimized with respect to solubility. ASTM G-85.5 (Prohesion™) is a cyclic corrosion test that more closely resembles real working environments. This accelerated corrosion test exposes samples to a cycle of fog of dilute salt and ammonium sulfate at room temperature followed by forced-air drying at an elevated temperature. This is a more realistic test of the ability of a compound to inhibit corrosion. Results of these tests can be combined to gain insight into how a particular coating or compound will perform relative to a standard as well as helping identify strengths and weaknesses in the performance of the material. [0766]
3) Rating Method [0767]
ASTM D-1654 evaluation standard for painted or coated specimens subjected to corrosive environments was used to evaluate the performance of the coatings. After the paint dried for 24 hours, each plate was scribed with an X and the plate edges were sealed with PVC tape to eliminate corrosion edge effects. [0768]
Two visual observations are associated with this rating test. Procedure A involves a rating of the failure at the scribe—the representative creepage of corrosion away from the scribe. Procedure B involves a rating of the failure in the unscribed areas in terms of the percentage which shows corrosion coming through the film. In this way, not only the bulk corrosion-inhibiting action of a pigment through the binder can be rated, but also its “throwing power”. [0769]
4) Comparison Examples [0770]
Zinc and strontium chromates are commercial CrVI-based pigments used extensively to provide corrosion protection to metal surfaces. These pigments were used as performance baselines to determine the effectiveness of permanganate-based pigment compositions developed using the methodology described in this specification. [0771]
Chromate pigments were precipitated from aqueous solutions and incorporated into PVB wash primer formulations so that each primer sample had the same molar quantity of hexavalent chromium. These primers were then applied to 2024-T3 and 7075-T6 aluminum alloy samples. After the-samples had dried for 24 hours, they were scribed and the-edges of each sample taped to eliminate edge effects. These samples were then exposed to 168 hours of both ASTM B-117 and G-85.5. Magnesium chromate is so soluble in aqueous solution that the resin began to cross-link immediately, even before the phosphoric acid diluent was added to the PVB pigment mixture. PVB based paints containing magnesium chromate pigments performed well initially (the first 4 days of the test) but began to degrade rapidly as the chromate was depleted. Insoluble bismuth chromate appeared to enhance the effects of corrosion and performed worse than PVB samples that contained no pigment. Zinc and strontium species with intermediate aqueous solubility provided the greatest corrosion inhibition of the chromate pigments when used in the PVB wash primer. [0772]
Table 7 presents the accelerated corrosion testing results for bare 2024-T3 and 7075-T6 aluminum alloy test panels treated with PVB combined with zinc and strontium chromate corrosion inhibiting pigments. For each pigment, the first row shows the results on 2024-T3, and the second row shows the results on 7075-T6. The zinc and strontium chromate treated samples performed well during their period of exposure as is expected from the current state-of-the-art. Minor differences in performance as a function of substrate composition were noted. [0773]

TABLE 7

Zinc and Strontium Chromate Pigment Accelerated Corrosion Test Results

2024-T3 7075-T6 2024-T3 7075-T6

B-117 B-117 G-85 G-85 Hours

Stabilizer Proc. A Proc. B Proc. A Proc. B Proc. A Proc. B Proc. A Proc. B 168

Zn as 1.35 g 10 9 9 9 10 9 9 9 168

zinc

chromate

10 9 9 9 10 9 9 9 168

Sr as 1.51 g 9 9 9 9 9 9 9 9 168

strontium

chromate

9 9 9 8 9 9 9 9 168
5) MnIII and MnIV Pigments in PVB Resin [0774]

MnIII- and MnIV-valence stabilizer compounds were synthesized using either published literature procedures, or standard organometallic synthesis techniques because optimized MnIII and MnIV corrosion-inhibiting pigment materials are not commercially available. The pigment syntheses were mainly aqueous-based precipitation techniques, although some pigments (i.e., those using some selected organic valence stabilizers) needed alcohol/water mixtures for the synthesis due to the low solubility of the valence stabilizer compound in pure water. Table 8 shows the MnIII- and MnIV-valence stabilizer combinations used for these optimized manganese-containing paints. As can be seen in Table 8, MnIII and MnIV pigments containing both inorganic and organic valence stabilizers were formed.

TABLE 8


Optimized Trivalent and Tetravalent Manganese Pigments Prepared

	Synthesis	Addendum
Pigment	Solvent	Ions	Synthesis Notes

Mn⁺³/phosphotungstate	H₂O	Sr, Ca	Other salts (Mg, Ba, &
[11-tungstophospho-			Zn) not formed
manganate(III)]
Mn⁺³/molybdate [9-	H₂O	Mg, Ca, Zn, Sr, Ba	All salts readily formed.
molybdo-manganate(III)]
Mn⁺³/iodate [Hexaiodato-	H₂O	H, Ca, Zn, Sr, Ba	H (acid) salt precip. from
manganate(III)]		mother liq.; precip. of Ca,
		Zn, Sr, and Ba salts; Mg
		salt not formed
Mn⁺³/vanadate [3-	H₂O	Na, Mg, Ca, Zn, Sr,	Na salt precip. from
vanado-manganate(III)]		Ba	mother liq.
Mn⁺³/Diethyldithio-	H₂O	SO₄ ⁻², PO₄ ⁻³, WO₄ ⁻²,
		MoO₄ ⁻²,
		phoshomolybdate
Mn⁺³/2-Mercapto-	i-PrOH/H₂O	SO₄ ⁻²	SO₄ ⁻²fm. from mother liq.
benzimidazole
Mn⁺³/8-Hydroxy-	i-PrOH/H₂O	SO₄ ⁻², PO₄ ⁻³	SO₄ ^{−2 fm. from mother}
guinoline			liq.; PO₄ ⁻³on anion addn.

Table 9 presents the accelerated corrosion testing results for bare 2024-T3 and 7075-T6 aluminum alloy test panels treated with inorganically stabilized MnIII and MnIV pigments in PVB, while Table 10 shows some organically stabilized manganese pigments. Table 9 shows the samples that were produced, as well as the pigment contained within them. Note that the molar concentration of MnIII or MnIV in these paints is much less than that in the zinc chromate primers (7.44×10 ⁻³M). This was done because the molecular weight of the MnIII or MnIV compounds exceeds that of zinc chromate, implying that a much larger mass would be necessary to achieve equal molar concentrations of MnIII or MnIV and CrVI. As can be seen in the corrosion exposure results, even with these much lower molar concentrations of MnIII or MnIV, the “optimized” pigments provided comparable or substantial corrosion protection compared to chromium. These pigments also outperformed by a significant margin those pigments (i.e., molybdates, tungstates, phosphates, borates, cyanamides) containing no inheremt oxidizer properties. For each pigment, the first row shows the performance of one sample under the specified conditions, and the second shows the performance of a duplicate sample under the same conditions. It is also interesting to note the change in performance for the MnIII/MnIV pigments just by altering the solubility control agents.

TABLE 9


Inorganically Stabilized MnIII and Mn IV Wash Primers Formulations

Stabilizer	Inhibitor	B-117	B-117	G-85	G-85
Solubility Control Agent	Conc. (M)	Proc. A	Proc. B	Proc. A	Proc. B	Hours

Ca as 1.42 g calcium	7.44 × 10⁻⁴	6	3	5	4	6	5	7	6	117
9-molybdomanganate	(10% of Cr)
		6	3	5	4	6	5	7	6	117
Zn as 1.48 g zinc	7.44 × 10⁻⁴	5	3	5	4	7	7	7	7	117
9-molybdomanganate	(10% of Cr)
		5	3	5	3	7	6	8	7	117
Sr as 1.53 g strontium	7.44 × 10⁻⁴	5	—	4	—	6	5	6	5	117
9-molybdomanganate	(10% of Cr)
		5	—	5	—	6	5	6	5	117
Ba as 1.64 g barium	1.64 × 10⁻⁴	4	—	3	—	7	6	8	7	117
9-molybdomanganate	(10% of Cr)
		4	—	3	—	7	6	7	6	117
Ba as 2.06 g barium	1.49 × 10⁻³	5	3	5	3	7	7	8	8	144
hexaiodatomanganate	(20% of Cr)
		5	3	5	3	8	8	7	7	144
Mg as 1.28 g	7.44 × 10⁻⁴	9	7	7	8	7	6	6	5	139
magnesium	(10% of Cr)
13-vanadatomanganate
		9	7	7	8	7	6	7	6	139
Ca as 1.32 g calcium	7.44 × 10⁻⁴	8	7	7	6	7	6	7	6	139
13-vanadatomanganate	(10% of Cr)
		8	7	7	6	7	6	7	6	139
Zn as 1.37 g zinc	7.44 × 10⁻⁴	8	9	7	8	7	6	7	6	139
13-vanadatomanganate	(10% of Cr)
		8	9	7	8	7	5	6	5	139
Sr as 1.42 g strontium	7.44 × 10⁻⁴	7	6	7	6	6	5	6	5	139
13-vanadatomanganate	(10% of Cr)
		7	6	7	6	6	6	6	6	139
Ba as 1.53 g barium	7.44 × 10⁻⁴	7	8	7	6	6	6	6	5	139
13-vanadatomanganate	(10% of Cr)
		7	7	7	6	7	6	6	5	139

TABLE 10


Organically Stabilized MnIII and Mn IV Wash Primers Formulations

Stabilizer/	Inhibitor	B-117	B-117	G-85	G-85
Solubility Control Agent	Conc. (M)	Proc. A	Proc. B	Proc. A	Proc. B	Hours

Mn⁺⁴/DEDT/	1.49 × 10⁻³	6	5	7	6	168
sulfate	(20% of Cr)
		6	5	7	5	168
Mn⁺⁴/DEDT/	1.49 × 10⁻³	7	5	8	7	168
phosphate	(20% of Cr)
		7	5	8	7	168
Mn⁺⁴/DEDT/	1.49 × 10⁻³	7	6	7	5	168
molybdate	(20% of Cr)
		7	6	7	5	168
Mn⁺⁴/DEDT/	1.49 × 10⁻³	7	5	7	5	168
tungstate	(20% of Cr)
		7	5	7	5	168
Mn⁺³/MBI/	1.49 × 10⁻³	7	7	6	6	168
sulfate	(20% of Cr)
		8	7	6	6	168
Mn⁺³/HQ/	1.49 × 10⁻³	6	5	6	5	168
sulfate	(20% of Cr)
		6	5	6	5	168
Mn⁺³/HQ/	1.49 × 10⁻³	7	6	8	7	168
phosphate	(20% of Cr)
		7	6	8	7	168

Table 10 shows the results for a few of the organic valence stabilizers evaluated. Due to low substrate supplies, these pigments were only tested on duplicate 2024-T3 aluminum alloy under both ASTM B-117 and G-85 conditions. The molar concentration of MnIII and MnIV in these pigments were also much less than in the standard chromate pigments. Clear progressions in the performance of these pigments as a function of anionic solubility control agents were also observed. [0778]
6) Calcined MnIII and MnIV Pigments [0779]
Calcined MnIII and MnIV pigments were prepared by mixing oxides, hydroxides, or peroxides of Mg, Ca, Sr, Ba, Zn, Bi, Co, Ni, or Fe with manganese oxides such as Mn[0780] ₂O₃or MnO₂and firing in air for up to four hours between 400 and 715° C.±10° C. The ceramic oxide pigments were mixed 1:1 by weight with boiled linseed oil. This mixture was painted on to bare 1008 carbon steel sheet that had been prepared with an alkaline cleaning treatment. An identical steel specimen was painted with red-lead (Pb3O4) and boiled linseed for use as a comparison standard. The painted test panels were allowed to dry for 48 hours, X scribed completely through the coating, and then exposed to ASTM B 117 for 41 hours.
The Ca-, Zn-, and Sr-containing pigments demonstrated corrosion inhibition performance equal to that of the of the red lead pigments in a side by side comparison. The Ba-containing pigment performed nearly as well as Ca, Zn, and Sr formulations by providing a high degree of surface protection but not quite as good as the red lead standard. [0781]
Chromium- or lead-free pigments based on MnIII and/or MnIV which can be used as replacements for the current CrVI or PbIV pigments can be made. Many synthesis methodologies and procedures are available for those skilled in the art of coordination compound synthesis to produce a multitude of MnIII and/or MnIV corrosion inhibiting pigments. One or two synthesis procedures or solvents are likely to be typical for specific MnIII- or MnIV-valence stabilizer combinations. The methodology described in this specification encompasses the entire range of valence stabilized MnIII or MnIV pigment formulations. [0782]
Pigments formed in accordance with the prior art are not competitive with the present invention. Prior art embodiments require the use of application processes and chemical compounds that do not form pigments containing valence stabilized MnIII- or MnIV-based active corrosion inhibitors that perform equivalent to current effective commercial hexavalent chromium- or tetravalent lead-based pigment systems. [0783]
While the invention has been described by reference to certain embodiments, it should be understood that numerous changes could be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the disclosed embodiments, but that it have the full scope permitted by the language of the following claims.[0784]

Claims

We claim:

1. A corrosion-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex.

2. The pigment of claim 1 wherein the manganese/valence stabilizer complex has a solubility in water of between about 1×10⁰and about 1×10⁻¹⁷moles per liter of manganese at about 25° C. and about 760 Torr.

3. The pigment of claim 2 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10⁻¹and about 1×10⁴moles per liter of manganese at about 25° C. and about 760 Torr.

4. The pigment of claim 2 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10⁻⁶and about 1×10⁻⁸moles per liter of manganese at about 25° C. and about 760 Torr.

5. The pigment of claim 2 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10⁻⁹and about 1×10⁻⁷moles per liter of manganese at about 25° C. and about 760 Torr.

6. The pigment of claim 1 wherein there is an electrostatic barrier layer around the manganese/valence stabilizer complex in aqueous solution.

7. The pigment of claim 1 wherein the manganese/valence stabilizer complex acts as an ion exchange agent towards corrosive ions.

8. The pigment of claim 1 wherein the manganese/valence stabilizer complex decomposes above about 100° C.

9. The pigment of claim 1 wherein the manganese/valence stabilizer complex melts above about 50° C.

10. The pigment of claim 1 wherein the valence stabilizer is an inorganic valence stabilizer or an organic valence stabilizer.

11. The pigment of claim 10 wherein the valence stabilizer is the inorganic valence stabilizer selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, antimonates, stannates, sulfates, polyphosphates, titanates, zirconates, oxygen, bismuthates, germinates, carbonates, arsenates, phosphates, borates, aluminates, silicates, or combinations thereof.

12. The pigment of claim 1 wherein the valence stabilizer is the inorganic valence stabilizer selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, oxygen, antimonates, stannates, sulfates, polyphosphates, titanates, zirconates, phosphates, borates, aluminates, silicates, or combinations thereof.

13. The pigment of claim 1 wherein the manganese/valence stabilizer complex has a central cavity containing a manganese ion and an additional ion.

14. The pigment of claim 13 wherein the additional ion is B⁺³, Al⁺³, Si⁺⁴, P⁺⁵, Ti⁺⁴, V⁺⁵, V⁺⁴, Cr⁺⁶, Cr⁺³, Mn⁺², Fe⁺³, Fe⁺², Co⁺², Co⁺³, Ni⁺², Ni⁺³, Ni⁺⁴, Cu⁺², Cu⁺³, Zn⁺², Ga⁺³, Ge⁺⁴, As⁺⁵, As⁺³, Zr⁺⁴, or Ce⁺⁴.

15. The pigment of claim 10 wherein the valence stabilizer is the organic valence stabilizer selected from monoamines; diamines; triamines; tetraamines; pentamines; hexamines; five- or six-membered heterocyclic rings containing one to four nitrogen atoms optionally having additional nitrogen, sulfur, or oxygen binding sites; five- or six-membered heterocyclic rings containing one or two sulfur atoms and having additional nitrogen binding sites; five- or six-membered heterocyclic rings containing one or two oxygen atoms and having additional nitrogen binding sites; (two-, three-, four-, six-, eight-, or ten-)membered nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; macrocyclic oligothioketones or dithiolenes; diazenes; thio-, amido-, or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; thio-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases containing at least two azo, imine, or azine groups; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; ortho- (for aryl) or alpha- or beta- (for alkyl) substituted azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; oximes; amidines and imido compounds; dithio ligands; amides; amino acids; N-(thio)acyl 7-aminobenzylidenimines; (thio)hydroxamates; alpha- or ortho-aminothio(di)carboxylic acids and salts; (thio)semicarbazones; (thio)acyl hydrazones; (thio)carbazones; silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl imines; (thio)aryl amines and imines; guanylureas; guanidinoureas; 2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines; 1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides; 2-acylthioacetamides; dithiodicarbonic diamides; trithiodicarboxylic acids and salts; monothiocarbamates; monothioethers; dithioethers; trithioethers; tetrathioethers; pentathioethers; hexathioethers; disulfides; monophosphines; diphosphines; triphosphines; tetraphosphines; pentaphosphines; hexaphosphines; five- or six-membered heterocyclic rings containing one or two sulfur atoms optionally having additional sulfur, oxygen, or phosphorus binding sites; five- or six-membered heterocyclic rings containing one to three phosphorus atoms optionally having additional phosphorus, nitrogen, oxygen, or sulfur binding sites; five- or six-membered heterocyclic rings containing one to four nitrogen atoms and having additional phosphorus binding sites; five- or six-membered heterocyclic rings containing one or two oxygen atoms and optionally having additional sulfur or phosphorus binding sites; (five-, seven-, or nine-)membered nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; (two- to ten-)membered sulfur, sulfur-oxygen, or sulfur-phosphorus macrocyclics, not including oligothioketones or dithiolenes; (two- to ten-)membered phosphorus, nitrogen-phosphorus, or oxygen-phosphorus macrocyclics; (two- to ten-)membered oxygen macrocyclics; thio-, amido-, or imido-derivatives of phosphonic and diphosphonic acids and salts containing no sulfur binding sites; amido-, or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts containing no sulfur binding sites; dithioperoxydiphosphoramides; dithioperoxydiphosphoric acids and salts; monothioperoxydiphosphoramides; monothioperoxydiphosphoric acids and salts; monothiophosphoric acids; phosphoro(dithioperoxoic) acids and salts; azo compounds, triazenes, formazans, azines, or Schiff Bases; silylamines; silazanes; guanidines and diguanidines; pyridinaldimines; hydrazones; hydramides; nitriles; thioureas and thioamides; ureas and pseudoureas; biurets; monothio ligands; diketone ligands; dithioperoxydicarbonic acids and salts; dithioacyl disulfides; tetrathioperoxydicarbonic diamides; (hexa-, penta-, or tetra-)thioperoxydicarbonic acids and salts; 1,2-dithiolates; rhodanines; dithiocarbimates; (thio)xanthates; S-(alkyl- or aryl-thio)thiocarboxylic acids and salts; phosphinodithioformates; (thio)borates and (thio)boronates; (thio)arsonic acids and salts; (thio)antimonic acids and salts; phosphine and arsine sulfides or oxides; beta-hydroxyketones and aldehydes; squaric acids and salts; carbonates; carbamates and carbimates; carbazates; imidosulfurous diamides; sulfurdiimines; thiocarbonyl and mercapto oximes; 2-nitrothiophenols; 2-nitrilo(thio)phenols; acylcyanamides; imidates; 2-amidinoacetates; beta-ketoamines; 3-aminoacrylamides and 3,3-diaminoacrylamides; 3-aminoacrylic acids and salts and 3-hydroxy-3-aminoacrylic acids and salts; 2-nitroanilines; amine and diazine N-oxides; hydrazides and semicarbazides; (amino- or imino-)aryl phosphines; (thio- or hydroxy-)aryl phosphines; arsines; five- or six-membered heterocyclic rings containing one arsenic atom optionally having additional arsenic binding sites;(two- to six-)membered arsenic macrocyclics; selenoethers; five- or six-membered heterocyclic rings containing one or two selenium atoms optionally having additional selenium binding sites; (two- to six-)membered selenium macrocyclics; 1,3-diselenoketones; 1,1-diselenolates; diselenocarbamates; selenophosphoric acids and salts; selenocarbonates; cyanide, isocyanide, and cyanamide ligands; nitrosyl and nitrite ligands; azide ligands; thiolates and selenolates; (thio)cyanate ligands; diene or bicyclic or tricyclic hydrocarbon ligands; carbonyl, halogen, oxo, and hydroxo ligands; or combinations thereof.

16. The pigment of claim 15 wherein the organic valence stabilizer is selected from monoamines; diamines; triamines; tetraamines; pentamines; hexamines; five- or six-membered heterocyclic rings containing one to four nitrogen atoms optionally having additional nitrogen, sulfur, or oxygen binding sites; five- or six-membered heterocyclic rings containing one or two sulfur atoms and having additional nitrogen binding sites; five- or six-membered heterocyclic rings containing one or two oxygen atoms and having additional nitrogen binding sites; (two-, three-, four-, six-, eight-, or ten-)membered nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; macrocyclic oligothioketones or dithiolenes; diazenes; thio-, amido-, or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases containing at least two azo, imine, or azine groups; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; ortho- (for aryl) or alpha- or beta- (for alkyl) substituted azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; oximes; amidines and imido compounds; dithio ligands; amides; amino acids; N-(thio)acyl 7-aminobenzylidenimines; (thio)hydroxamates; alpha- or ortho-aminothio(di)carboxylic acids and salts; (thio)semicarbazones; (thio)acyl hydrazones; (thio)carbazones; silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl imines; (thio)aryl amines and imines; guanylureas; guanidinoureas; biurets; diketone ligands; amido- or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; beta-hydroxyketones and -aldehydes; squaric acids and salts; carbamates and carbimates; 2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines; 1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides; 2-acylthioacetamides; dithiodicarbonic diamides; trithiodicarboxylic acids and salts; monothiocarbamates; (thio)cyanate ligands; oxo and hydroxo ligands; or combinations thereof.

17. The pigment of claim 15 wherein the organic valence stabilizer is the diazene selected from diazeneformimidamides, diazeneformamides, diazenefonmothioamides, diazeneacetimidamides, diazeneacetothioamides, diazeneformimidic acids and salts, diazeneacetimidic acids and salts, diazenecarbothioic acids and salts, diazenecarbodithioic acids and salts, diazeneformimidothioic acids and salts, diazeneformaldehydes, diazeneformothioaldehydes, diazeneacetaldehydes, diazeneacetothioaldehydes, diazenediformamides, diazenediformothioamides, diazenediacetamides, diazenediacetothioamides, diazeneacetimidothioic acids and salts, imidoyldiazenes, diazenediformimidamides, diazenediacetimidamides, diazenediformimidic acids and salts, diazenediacetimidic acids and salts, diazenediformimidothioic acids and salts, diazenediacetimidothioic acids and salts, diazenedicarbothioic acids, diazenedicarbodithioic acids, diazeneformic acids, diazenediformic acids, diazeneacetic acids, diazenediacetic acids, diazenediformaldehydes, diazenediformothioaldehydes, diazenediacetaldehydes, diazenediacetothioaldehydes, diimidoyldiazenes, or combinations thereof.

18. The pigment of claim 15 wherein the organic valence stabilizer is the thio-, amido-, or imido-derivative of hypophosphoric, phosphoric, or diphosphoric acids and salts selected from phosphoramidimidic triamides, phosphoramidimidic acids and salts, phosphorodiamidimidic acids and salts, phosphorodiamidimidothioic acids and salts, phosphoramidimidothioic acids and salts, phosphorodiamidimidodithioic acids and salts, phosphoramidimidodithioic acids and salts, (di- or mono-)thiohypophospboric acids and salts, (di- or mono-)thiohypophosphoramides, phosphoramidic acids and salts, phosphorimidic acids and salts, (di- or mono-)thioimidodiphosphoric acids and salts, (di- or mono-)thiohydrazidodipbosphoric acids and salts, (di- or mono-)thioimidodiphosphoramides, (di- or mono-)thiohydrazidodiphosphoramides, phosphoric triamides, (di- or mono-)thiodiphosphoramides, (di- or mono-)thiodiphosphoric acids and salts, (tetra-, tri-, di-)thiophosphoric acids and salts, phosphoro(dithioperoxo)(mono-,di-, or tri-)thioic acids and salts, phosphorimido(mono-, di-, or tri-)thioic acids and salts, phosphorothioic triamides, phosphoramido(mono, di- or tri-)thioic acids and salts, phosphorodiamido(mono, di- or tri-)thioic acids and salts, or combinations thereof.

19. The pigment of claim 15 wherein the organic valence stabilizer is a substituent for the ortho- (for aryl) or alpha- or beta- (for alkyl) substituted azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases selected from amino, imino, oximo, diazeno, hydrazido, thiol, mercapto, thiocarbonyl, hydroxy, carbox, and carbonyl substituents, or combinations thereof.

20. The pigment of claim 15 wherein the organic valence stabilizer is the oxime selected from monooximes, dioximes, carbonyl oximes, imine oximes, hydroxy oximes, amino oximes, amido oximes, hydrazone oximes, azo oximes, or combinations thereof.

21. The pigment of claim 15 wherein the organic valence stabilizer is the amidine and imido compound selected from amidines, diamidines, biguamides, biguanidines, diamidinomethanes, imidoylguanidines, amidinoguanidines, diformamidine oxides, sulfides, and disulfides, imidodicarbonimidic acids and salts, diimidodicarbonimidic acids and salts, thioimidodicarbonimidic acids and salts, thiodiimidodicarbonimidic acids and salts, diimidoylimines, diimidoylhydrazides, imidosulfamides, diimidosulfamides, O-amidinocarbamates, O- or S-amidino(mono-, di-, or peroxy-)thiocarbamates, N-hydroxy(or N,N′-dihydroxy)amidines, diimidosulfuric acids and salts, or combinations thereof.

22. The pigment of claim 15 wherein the organic valence stabilizer is the dithio ligand selected from dithioimidodialdehydes, dithiohydrazidodialdehydes, dithioimidodicarbonic acids and salts, dithiohydrazidodicarbonic acids and salts, 1,3-dithioketones, 1,2-dithioketones, dithiomalonamides, 2-thioacylthioacetamides, dithioacyl sulfides, trithiodicarbonic diamides, (penta-, tetra-, tri-)thiodicarbonic acids and salts, beta-mercaptothioketones and -aldehydes, N-(aminomethylthiol)thioureas, dithiooxamides, 1,1-dithiolates, (di- or per-)thiomonocarboxylic acids and salts, (tetra- or per-)thiodicarboxylic acids and salts, (di-, tri-, or per-)thiocarbonates, dithiocarbamates (including N-hydroxydithiocarbamates and N-mercaptodithiocarbamates), dithiocarbazates, or combinations thereof.

23. The pigment of claim 15 wherein the organic valence stabilizer is the amide selected from monoamides, lactams, amidinoamides, guanidinoamides, imidoylamides, polyamides, polylactams, or combinations thereof.

24. The pigment of claim 15 wherein the organic valence stabilizer is the thio-, amido-, or imido-derivative of phosphonic and diphosphonic acids and salts selected from phosphonitrile amides, phosphonimidic diamides, phosphonamidimidic acids and salts, phosphonamidimidothioic acids and salts, dithioimidodiphosphonic acids and salts, dithiohydrazidodiphosphonic acids and salts, dithioimidodiphosphonamides, dithiohydrazidodiphosphonamides, dithiodiphosphonamides, dithiodiphosphonic acids and salts, dithioperoxydiphosphonamides, dithioperoxydiphosphonic acids and salts, (di- and tri-)thiophosphonic acids and salts, phosphono(dithioperoxo)thioic acids and salts, phosphono(dithioperoxo)dithioic acids and salts, phosphonimidothioic acids and salts, phosphonimidodithioic acids and salts, phosphonothioic acids and salts, phosphonanidothioic acids and salts, phosphonamidimidodithioic acids and salts, monothioimidodiphosphonic acids and salts, monothiohydrazidodiphosphonic acids and salts, monothioimidodiphosphonamides, monothiohydrazidodiphosphonamides, monothiodiphosphonamides, monothiodiphosphonic acids and salts, monothioperoxydiphosphonamides, monothioperoxydiphosphonic acids and salts, monothiophosphonic acids and salts, phosphono(dithioperoxoic) acids and salts, or combinations thereof.

25. The pigment of claim 15 wherein the organic valence stabilizer is the amido- or imido-derivative of hypophosphoric, phosphoric, or diphosphoric acids and salts containing no sulfur binding sites selected from hypophosphoric acids and salts, hypophosphoramides, imidodiphosphoric acids and salts, hydrazidodiphosphoric acids and salts, imidodiphosphoramides, hydrazidodiphosphoramides, diphosphoramides, or combinations thereof.

26. The pigment of claim 15 wherein the organic valence stabilizer is the amido- or imido-derivative of phosphonic or diphosphonic acids and salts containing no sulfur binding sites selected from imidodiphosphonic acids and salts, hydrazidodiphosphonic acids and salts, imidodiphosphonamides, hydrazidodiphosphonamides, diphosphonamides, phosphonimidic acids and salts, phosphonamidic acids and salts, phosphonic diamides, or combinations thereof.

27. The pigment of claim 15 wherein the organic valence stabilizer is the thiourea and thioamide selected from thioureas, thiocarboxamides, thioacylthioureas, acylthioureas, thioacylureas, thioaroylthioureas, aroylthioureas, thioaroylureas, thioimidates, thioguanylureas, guanidinothioureas, amidinothioamides, guanidinothioamides, imidoylthioamides, 3-aminothioacrylamides, thiohydrazides, thiosemicarbazides, (mono- and di-)thiobiurets, (mono- and di-)thioisobiurets, (mono- and di-)thiobiureas, N-(aminomethylol)thioureas, N-(aminomethylthiol)ureas, beta-mercaptocarboxamides, or combinations thereof.

28. The pigment of claim 15 wherein the organic valence stabilizer is the biuret selected from biurets, triurets, isobiurets, biureas, triureas, acylureas, aroylureas, N-(aminomethylol)ureas, or combinations thereof.

29. The pigment of claim 15 wherein the organic valence stabilizer is the monothio ligand selected from beta-aminothiones, 3-aminothioacrylic acids and salts, 3-mercapto-3-aminothioacrylic acids and salts, N-thioacyl benzylidenimines, thioimidodialdehydes, thiohydrazidodialdehydes, thioimidodicarbonic acids and salts, thiohydrazidodicarbonic acids and salts, 1,2-monothioketones, trithioperoxydicarbonic diamides, dithioperoxydicarbonic diamides, dithiodicarbonic acids and salts, trithioperoxydicarbonic acids and salts, beta-hydroxythioketones, beta-hydroxythioaldehydes, beta-mercaptoketones, beta-mercaptoaldehydes, monothiooxamides, beta-mercaptocarboxylic acids and salts, beta-mercaptothiocarboxylic acids and salts, beta-hydroxythiocarboxylic acids and salts, S-alkylthiocarboxylic acids and salts, S-arylthiocarboxylic acids and salts, S-alkyldisulfidocarboxylic acids and salts, S-aryldisulfidocarboxylic acids and salts, monothiomonocarboxylic acids and salts, dithiodicarboxylic acids and salts, monothiocarbonates, monothiocarbazates, monothiocarbimates, mercaptoalcohols, silylmercaptoalcohols, or combinations thereof.

30. The pigment of claim 15 wherein the organic valence stabilizer is the diketone ligand selected from imidodialdehydes, hydrazidodialdehydes, imidodicarbonic acids and salts, hydrazidodicarbonic acids and salts, imidodisulfamic acids and salts, imidodisulfuric acids and salts, 1,3-diketones, 1,3,5-triketones, 1,2-diketones, 1,2,3-triketones, tropolonates, ortho-quinones, malonamides, 2-acylacetamides, monothiodicarbonic diamides, monothiodicarbonic acids and salts, trithionic acids and salts, oxamides, dicarboxylic acids, or combinations thereof.

31. The pigment of claim 15 wherein the organic valence stabilizer is the S-(alkyl- or aryl-thio)thiocarboxylic acid and salt selected from S-(alkylthio)thiocarboxylic acids and salts, S-(arylthio)thiocarboxylic acids and salts, S,S-thiobisthiocarboxylic acids and salts, S-(alkyldisulfido)thiocarboxylic acids and salts, S-(aryldisulfido)thiocarboxylic acids and salts, S,S′-disulfidobisthiocarboxylic acids and salts, or combinations thereof.

32. The pigment of claim 15 wherein the organic valence stabilizer is the phosphine and arsine sulfide or oxide selected from phosphine P-sulfides, aminophosphine sulfides, arsine As-sulfides, aminoarsine sulfides, phosphine P-oxides, aminophosphine oxides, arsine As-oxides, aminoarsine oxides, or combinations thereof.

33. The pigment of claim 15 wherein a solubility in water of the manganese/valence stabilizer complex is adjusted by an addition of a substituent group on the organic valence stabilizer.

34. The pigment of claim 33 wherein the solubility in water is increased by the addition of the substituent group selected from sulfonate groups (—SO₃ ⁻), carboxyl groups (—CO₂—), hydroxyl groups (—OH), ester groups (—CO₃—), carbonyl groups (═C═O), amine groups (—NH₂), nitrosamine groups (═N—N═O), carbonylnitrene groups (—CO—N), sulfoxide groups (═S═O), sulfone groups (═S[═O]₂), sulfinyl groups (—N═S═O), sulfodiimines (═S[=NH]₂), sulfonyl halide groups (—S[═O]₂X), sulfonamide groups (—S[═O]₂NH₂), monohalosulfonamide groups (—S[═O]₂NHX), dihalosulfonamide groups (—S[═O]₂MX₂), halosulfonate groups (—S[═O]₂OX), halosulfonate amide groups (═N—S[═O]₂X), aminosulfonate groups (═N—S[═O]₂OH), iminosulfonate groups (—N[SO₃ ⁻]_1-2), phosphonate groups (PO₃ ⁻²), phosphonamide groups (—PO₂NH₂ ⁻), phosphondiamide groups (—PO[NH₂]₂), aminophosphonate groups (═N—PO₃ ⁻²), iminophosphonate groups (—N[PO₃ ⁻²]_1-2), or combinations thereof.

35. The pigment of claim 33 wherein the solubility in water is decreased by the addition of the substituent group selected from nitro groups (—NO₂), perfluoroalkyl groups (—C_xF_2x+1), perchloroalkyl groups (—C_xCl_2x+1), nitramine groups (═N—NO₂), thioketone groups (═C═S), sulfenyl halide groups (—S—X), sulfur dihaloimide groups (—N═SX₂), or combinations thereof.

36. The pigment of claim 15 wherein an electrostatic barrier layer of the manganese/valence stabilizer complex is adjusted by an addition of a substituent group on the organic valence stabilizer.

37. The pigment of claim 36 wherein the electrostatic barrier layer is increased by the addition of the substituent group selected from ketones (═C═O), thioketones (═C═S), amides (—C[═O]NR₂), thioamides (—C[═S]—NR₂), nitriles or cyano groups (—CN), isocyanides (—NC), nitroso groups (—N═O), thionitroso groups (—N═S), nitro groups (—NO₂), azido groups (—N₃), cyanamide or cyanonitrene groups (═N—CN), cyanate groups (—O—CN), isocyanate groups (—N═C═O), thiocyanate groups (—S—CN), isothiocyanate groups (—N═C═S), nitrosamine groups (═N—N═O), thionitrosamine groups (═N—N═S), nitramine groups (═N—NO₂), thionitramine groups (═N—NS₂), carbonylnitrene groups (—CO—N), thiocarbonylnitrene groups (—CS—N), sulfenyl halides (—S—X), sulfoxides (═S═O), sulfones (═S[═O]₂), sulfinyl groups (—N═S═O), thiosulfinyl groups (—N═S=S), sulfenyl thiocyanato groups (—S—S—CN), sulfenyl cyanato groups (—S—O—CN), sulfodiimine groups (═S[=NH]₂), sulfur dihaloimido groups (—N═SX₂), sulfur oxide dihaloimido groups (—N═S[═O]X₂), aminosulfur oxide trihalide groups (═N—S[═O]X₃), sulfonyl azide groups (—S[═O]₂N₃), sulfonyl thiocyanate groups (—S[═O]₂SCN), sulfonyl cyanate groups (—S[═O]₂OCN), sulfonyl cyanide groups (—S[═O]₂CN), halosulfonate groups (—S[═O]₂OX), phosphonyl thiocyanate groups (—P[═O]OHSCN), phosphonyl cyanate groups (—P[═O]OHOCN), phosphonyl cyanide groups (—P[═O]OHCN), or combinations thereof.

38. The pigment of claim 1 further comprising a solubility control agent.

39. The pigment of claim 38 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.

40. The pigment of claim 39 wherein the solubility control agent is the cationic solubility control agent selected from H⁺; Li⁺; Na⁺; K⁺; Rb⁺; Cs⁺; NH₄ ⁺; Mg⁺²; Ca⁺²; Sr⁺²; Be⁺²; Ba⁺²; Y⁺³; La⁺³; Ce⁺³; Ce⁺⁴; Nd⁺³; Pr⁺³; Sc⁺³; Sm⁺³; Eu⁺³; Eu⁺²; Gd⁺³; Tb⁺³; Dy⁺³; Ho⁺³; Er⁺³; Tm⁺³; Yb⁺³; Lu⁺³; Ti⁺⁴; Zr⁺⁴; Ti⁺³; Hf⁺⁴; Nb⁺⁵; Ta⁺⁵; Nb⁺⁴; Ta⁺⁴; V⁺⁵; V⁺⁴; V⁺³; Mo⁺⁶; W⁺⁶; Mo⁺⁵; W⁺⁵; Mo⁺⁴; W⁺⁴; Cr⁺³; Mn⁺²; Mn⁺³; Mn⁺⁴; Fe⁺²; Fe⁺³; Co⁺²; Co⁺³; Ni⁺²; Ni⁺³; Ni⁺⁴; Ru⁺²; Ru⁺³; Ru⁺⁴; Ru⁺³; Ir⁺³; Rh⁺²; Ir⁺²; Pd⁺⁴; Pt⁺⁴; Pd⁺²; Pt⁺²; Os⁺⁴; Cu⁺; Cu⁺²; Cu⁺³: Ag⁺; Ag⁺²; Ag⁺³; Au⁺; Au⁺²; Au⁺³; Zn⁺²; Cd⁺²; Hg⁺; Hg⁺²; Al⁺³; Ga⁺³; Ga⁺; In⁺³; In⁺; Tl⁺³; Tl⁺; Ge⁺⁴; Ge⁺²; Sn⁺⁴; Sn⁺²; Pb⁺⁴; P⁺²; Sb⁺³; Sb⁺⁵; As⁺³; As⁺⁵; Bi⁺³; Bi⁺⁵; organic compounds containing at least one N⁺ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one arsonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one selenonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR₄ ⁺, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.

41. The pigment of claim 40 wherein the cationic solubility control agent is selected from H⁺; Li⁺; Na⁺; K⁺; Rb⁺; Cs⁺; NH₄ ⁺; Mg⁺²; Ca⁺²; Sr⁺²; Y⁺³; La⁺³; Ce^{+3; Ce} ⁺⁴; Nd⁺³; Pr^{+3; Sc} ⁺³; Sm⁺³; Eu⁺³; Eu⁺²; Gd⁺³; Tb⁺³; Dy⁺³; Ho⁺³; Er⁺³; Tm⁺³; Yb⁺³; Lu⁺³; Ti⁺⁴; Zr⁺⁴; Ti⁺³; Zr⁺⁴; Ti⁺³; Hf⁺⁴; Nb⁺⁵; Ta⁺⁵; Nb⁺⁴, Ta⁺⁴; Mo⁺⁶; W⁺⁶; Mo⁺⁵; W⁺⁵; Mo⁺⁴; W⁺⁴; Mn⁺²; Mn⁺³; Mn⁺⁴Fe⁺²; F⁺³; Co⁺²; Co⁺³; Ru⁺²; Ru⁺³; Ru⁺⁴; Rh⁺³; Ir⁺³; Rh⁺²; Ir⁺²; Pd⁺⁴; Pt⁺⁴; Pd⁺²; Pt⁺²; Cu⁺; Cu⁺²; Cu⁺³; Ag⁺; Ag⁺²; Ag⁺³; Au⁺; Au⁺³; Au^{+3+; Zn} ^'2; Al⁺³; Ga⁺³; Ga⁺; In⁺³; In⁺; Ge⁺⁴; Ge⁺²; Sn⁺⁴; Sn⁺²; Sb⁺³; Sb⁺⁵; Bi⁺³; Bi⁺⁵; organic compounds containing at least one N⁺ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR₄ ⁺, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.

42. The pigment of claim 39 wherein the solubility control agent is the anionic solubility control agent selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoroinanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions, chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, vanadates, or combinations thereof.

43. The pigment of claim 42 wherein the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, or combinations thereof.

44. The pigment of claim 1 wherein the manganese/valence stabilizer complex is adsorbed or mixed onto, into, or with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof.

45. The pigment of claim 1 wherein the pigment is colored.

46. The pigment of claim 1 wherein the pigment exhibits a color change between manganese oxidation states.

47. The pigment of claim 1 wherein the pigment is light-fast.

48. A method of making a corrosion-inhibiting pigment comprising:

providing a solvent;

providing a manganese source in the solvent forming a manganese solution;

providing a valence stabilizer; and

combining the manganese source and the valence stabilizer to form a manganese/valence stabilizer complex.

49. The method of claim 48 wherein the manganese source is selected from divalent manganese sources, trivalent manganese sources, tetravalent manganese sources, heptavalent manganese sources, or combinations thereof.

50. The method of claim 48 further comprising oxidizing the manganese source.

51. The method of claim 50 wherein the manganese source is oxidized by adding an oxidizer to the manganese solution.

52. The method of claim 51 wherein the oxidizer is a dissolved solid, a liquid, or a gas.

53. The method of claim 51 wherein the oxidizer is selected from peroxides, superoxides, persulfates, perborates, pernitrates, perphosphates, percarbonates, persilicates, peraluminates, pertitanates, perzirconates, permolybdates, pertungstates, pervanadates, organic peroxyacid derivatives, ozone, hypochlorites, chlorates, perchlorates, nitrates, nitrites, vanadates, iodates, hypobromites, chlorites, bromates, permanganates, periodates, dissolved oxygen, dissolved chlorine, dissolved fluorine, or combinations thereof.

54. The method of claim 50 wherein the manganese source is oxidized by electrolysis.

55. The method of claim 48 wherein the manganese/valence stabilizer complex is formed by a process selected from precipitation, evaporation, salting out with chemicals, freezing, freeze drying, or firing at an elevated temperature.

56. The method of claim 55 wherein the manganese/valence stabilizer complex is formed by precipitation.

57. The method of claim 48 wherein the manganese source is selected from manganese oxide, manganese dioxide, manganomanganic oxide, manganese sesquioxide, manganese hydroxide, manganese carbonate, manganese silicate, manganese borate, manganese sulfide, manganese phosphate, lithiated manganese spinel, manganese oxalate, manganese nitrate, manganese sulfate, manganese perchlorate, manganese chloride, manganese fluoride, manganese bromide, manganese iodide, manganese bromate, manganese chlorate, manganese fluosilicate, manganese fluotitanate, manganese fluozirconate, manganese fluoborate, manganese fluoaluminate, manganese formate, manganese acetate, manganese propionate, manganese butyrate, manganese valerate, manganese benzoate, manganese glycolate, manganese lactate, manganese tartronate, manganese malate, manganese tartrate, manganese citrate, manganese benzenesulfonate, manganese thiocyanate, manganese acetylacetonate, potassium permanganate, sodium permanganate, lithium permanganate, ammonium permanganate, magnesium permanganate, calcium permanganate, strontium permanganate, barium permanganate, zinc permanganate, ferric permanganate, nickel permanganate, copper permanganate, cobalt permanganate, cerium permanganate, lanthanum permanganate, yttrium permanganate, aluminum permanganate, or combinations thereof.

58. The method of claim 48 wherein the solvent comprises water.

59. The method of claim 48 wherein the solvent comprises an organic solvent.

60. The method of claim 59 wherein the organic solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, benzyl alcohol, glycerol, ethylene glycol, propylene glycol, cresol, cyclohexanol, butyl Carbitol, Cellosolve, methyl Cellosolve, ethyl lactate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, diethyl ether, isopropyl ether, furan, tetrahydrofuran, dioxane, tetrahydropyran, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, propylene oxide, acetic acid, propionic acid, butyrolactone, ethylene carbonate, propylene carbonate, benzaldehyde, propyl amine, diethyl amine, ethanolamine, aniline, pyridine, acetonitrile, dimethylformamide, propionitrile, nitrobenzene, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, benzene, toluene, xylene, mineral spirits, kerosene, gasoline, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, Freon 113, Stoddard's solvent, carbon disulfide, dimethyl sulfoxide, hexamethylphosphoric triamide, or combinations thereof.

61. The method of claim 48 wherein the valence stabilizer is an inorganic valence stabilizer or an organic valence stabilizer.

62. The method of claim 48 further comprising providing a solubility control agent.

63. The method of claim 62 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.

64. The method of claim 63 wherein the solubility control agent is the cationic solubility control agent selected from H⁺; Li⁺; Na⁺; K⁺; Rb⁺; Cs⁺; NH₄ ⁺; Mg⁺²; Ca⁺²; Sr⁺²; Be⁺²; Ba⁺²; Y⁺³; La⁺³; Ce⁺³; Ce⁺⁴; Nd⁺³; Pr⁺³; Sc⁺³; Sm⁺³; Eu⁺³; Eu⁺²; Gd⁺³; Tb⁺³; Dy⁺³; Ho⁺³; Er⁺³; Tm⁺³; Yb⁺³; Lu⁺³; Ti⁺⁴; Zr⁺⁴; Ti⁺³; Hf⁺⁴; Nb⁺⁵; Ta⁺⁵; Nb⁺⁴; Ta⁺⁴; V⁺⁵; V⁺⁴; V⁺³; Mo⁺⁶; W⁺⁶; Mo⁺⁵W⁺⁵; Mo⁺⁴; W⁺⁴; Cr⁺³; Mn⁺²; Mn⁺³; Mn⁺⁴; Fe⁺²; Fe⁺³; Co⁺²; Co⁺³; Ni⁺²; Ni⁺³; Ni⁺⁴; Ru⁺²; Ru⁺³; R⁺⁴; Rh^'3; Ir⁺³; Rh⁺²; Ir⁺²; Pd⁺⁴; Pt⁺⁴; Pd⁺²; Pt⁺²; Os⁺⁴; Cu⁺; Cu⁺²; Cu⁺³; Ag⁺; Ag⁺²; Ag⁺³; Au⁺; Au⁺²; Au⁺³; Zn⁺²; Cd⁺²; Hg⁺; Hg⁺²; Al⁺³; Ga⁺³; Ga⁺; In⁺³; In⁺; Tl⁺³; Tl⁺; Ge⁺⁴; Ge⁺²; Sn⁺⁴; Sn⁺²; Pb⁺⁴; Pb⁺²; Sb⁺³; Sb⁺⁵; As⁺³; As⁺⁵; Bi⁺³; Bi⁺⁵; organic compounds containing at least one N⁺ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one arsonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one selenonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR₄ ⁺, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.

65. The method of claim 64 wherein the cationic solubility control agent is selected from H⁺; Li⁺; Na⁺; K⁺; Rb⁺; Cs⁺; NH₄ ⁺; Mg⁺²; Ca⁺²; Sr⁺²; Y⁺³; La⁺³; Ce⁺³; Ce⁺⁴; Nd⁺³; Pr⁺³; Sc⁺³; Sm⁺³; Eu⁺³; Eu⁺²; Gd⁺³; Tb⁺³; Dy⁺³; Ho⁺³; Er⁺³; Tm⁺³; Yb⁺³; Lu⁺³; Ti⁺⁴; Zr⁺⁴; Ti⁺³; Hf⁺⁴; Nb⁺⁵; Ta⁺⁵; Nb⁺⁴; Ta⁺⁴; Mo⁺⁶; W⁺⁶; Mo⁺⁵; W⁺⁵; Mo⁺⁴; W⁺⁴; Mn⁺²; Mn⁺³; Mn⁺⁴; Fe⁺²; Fe⁺³; Co⁺²; Co⁺³; Ru⁺²; Ru⁺³; Ru⁺⁴; Rh⁺³; Tl⁺³; Rh⁺²; Ir⁺²; Pd⁺⁴; Pt⁺⁴; Pd⁺²; Pt⁺²; Cu⁺; Cu⁺²; Cu⁺³; Ag⁺; Ag⁺²; Ag⁺³; Au⁺; Au⁺²; Au⁺³; Zn⁺²; Al⁺³; Ga⁺³; Ga⁺; In⁺³; In⁺; Ge⁺⁴; Ge⁺²; Sn⁺⁴; Sn⁺²; Sb⁺³; Sb⁺⁵; Bi⁺³; Bi⁺⁵; organic compounds containing at least one N⁺ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR⁴ ⁺, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.

66. The method of claim 63 wherein the solubility control agent is the anionic solubility control agent selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions, chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, vanadates, or combinations thereof.

67. The method of claim 66 wherein the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di (thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonami des, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, or combinations thereof.

68. The method of claim 48 wherein the valence stabilizer is provided by adding it to the manganese solution.

69. The method of claim 48 wherein the valence stabilizer is provided as a separate solution.

70. The method of claim 62 wherein the solubility control agent is provided by adding the solubility control agent to the manganese solution.

71. The method of claim 62 whereby the solubility control agent is provided by adding the solubility control agent to a separate solution containing the valence stabilizer.

72. The method of claim 62 wherein the solubility control agent is provided as a separate solution.

73. The method of claim 48 further comprising heating the manganese solution.

74. The method of claim 48 further comprising cooling the manganese solution.

75. The method of claim 48 further comprising adjusting the pH of the manganese solution using a compound selected from acids or bases.

76. The method of claim 48 further comprising adsorbing or mixing the manganese/valence stabilizer complex onto, into, or with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof.

77. A method of making a corrosion-inhibiting pigment comprising:

providing a manganese source;

providing a valence stabilizer; and

heating the manganese source and the valence stabilizer in an oxidizing environment to form a pigment containing trivalent or tetravalent manganese.

78. The method of claim 77 wherein the manganese source is selected from divalent manganese sources, trivalent manganese sources, tetravalent manganese sources, heptavalent manganese sources, or combinations thereof.

79. The method of claim 77 wherein the manganese source is selected from manganese oxide, manganese dioxide, manganomanganic oxide, manganese sesquioxide, manganese hydroxide, manganese carbonate, manganese silicate, manganese borate, manganese sulfide, manganese phosphate, lithiated manganese spinel, manganese oxalate, manganese nitrate, manganese sulfate, manganese perchlorate, manganese chloride, manganese fluoride, manganese bromide, manganese iodide, manganese bromate, manganese chlorate, manganese fluosilicate, manganese fluotitanate, manganese fluozirconate, manganese fluoborate, manganese fluoaluminate, manganese formate, manganese acetate, manganese propionate, manganese butyrate, manganese valerate, manganese benzoate, manganese glycolate, manganese lactate, manganese tartronate, manganese malate, manganese tartrate, manganese citrate, manganese benzenesulfonate, manganese thiocyanate, manganese acetylacetonate, potassium penmanganate, sodium permanganate, lithium permanganate, ammonium penmanganate, magnesium permanganate, calcium permanganate, strontium permanganate, barium permanganate, zinc permanganate, ferric permanganate, nickel permanganate, copper penmanganate, cobalt penmanganate, cerium penmanganate, lanthanum permanganate, yttrium penmanganate, aluminum permanganate, or combinations thereof.

80. The method of claim 77 wherein the manganese source is a precipitate or a mineral.

81. The method of claim 80 wherein the manganese mineral is selected from manganosite, pyrochroite, rhodochrosite, rhodonite, tephroite, manganhumite, manganjustite, alabandite, hauerite, reddingite, hureaulite, pyrolusite, hausmannite, manganite, ramsdellite, bixbyite, groutite, feitknechite, akhtenskite, buserite, nsutite, hetaerolite, marokite, hydrohetaerolite, braunite, psilomelane, romanechite, cryptomelane, manjiroite, lithiophorite, chalcophanite, hollandite, neltnerite, woodruffite, birnesite, asbolane, todorokite, vernadite, or combinations thereof.

82. The method of claim 77 wherein the valence stabilizer is oxygen.

83. The method of claim 77 wherein the oxidizing environment is selected from oxygen, air, ozone, nitrogen oxides, sulfur oxides, chlorine, fluorine, or combinations thereof.

84. The method of claim 83 wherein the oxidizing environment is selected from oxygen, air, or combinations thereof.

85. The method of claim 77 wherein the manganese-containing mixture is heated to between about 200° C. and about 1200° C.

86. The method of claim 77 further comprising providing a solubility control agent.

87. The method of claim 86 wherein the solubility control agent is a cationic solubility control agent selected from Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be⁺², Mg⁺², Ca⁺², Sr^'2, Ba⁺², Y⁺³, La⁺³, Ce⁺³, Ce⁺⁴, Ti⁺⁴, Zr⁺⁴, V⁺⁵, Nb⁺⁵, Ta⁺⁵, Mo⁺⁶, W⁺⁶, Cr⁺³, Mn⁺², Fe⁺³, Fe⁺², Co⁺², Co⁺³, Ni⁺², Cu⁺², Ag⁺, Ag⁺², Zn⁺², Al⁺³, In⁺³, Sn⁺⁴, Sb⁺³, Sb⁺⁵, Bi⁺³, Bi⁺⁵, or combinations thereof.

88. The method of claim 87 wherein the cationic solubility control agent is selected from Ba⁺², Bi⁺³, Bi⁺⁵, or combinations thereof.

89. The method of claim 86 wherein the solubility control agent is provided by adding the solubility control agent to the manganese-containing mixture.

90. The method of claim 77 further comprising mixing the manganese/valence stabilizer complex onto, into, or with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, or combinations thereof.

91. A method for treating a surface for corrosion resistance, comprising:

providing a substrate to be coated; and

applying a corrosion-inhibiting pigment comprising manganese, where the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex.

92. The method of claim 91 wherein the substrate is subject to water-based electrochemical corrosion.

93. The method of claim 91 wherein the manganese/valence stabilizer complex has a solubility in water of between about 1×10⁰and about 1×10⁻¹⁷moles per liter of manganese at about 25° C. and about 760 Torr.

94. The method of claim 93 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10⁻¹and about 1×10⁴moles per liter of manganese at about 25° C. and about 760 Torr.

95. The method of claim 93 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10⁻⁶and about 1×10⁻⁸moles per liter of manganese at about 25° C. and about 760 Torr.

96. The method of claim 93 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10⁻⁹and about 1×10¹⁷moles per liter of manganese at about 25° C. and about 760 Torr.

97. The method of claim 91 wherein there is an electrostatic barrier layer around the manganese/valence stabilizer complex in aqueous solution.

98. The method of claim 91 wherein the manganese/valence stabilizer complex acts as an ion exchange agent towards corrosive ions.

99. The method of claim 91 wherein the manganese/valence stabilizer complex decomposes at a temperature above about 100° C.

100. The method of claim 91 wherein the manganese/valence stabilizer complex melts at a temperature above about 50° C.

101. The method of claim 91 wherein the valence stabilizer is an inorganic valence stabilizer or an organic valence stabilizer.

102. The method of claim 93 wherein the manganese/valence stabilizer complex further comprises a solubility control agent.

103. The method of claim 102 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.

104. The method of claim 103 wherein the solubility control agent is the cationic solubility control agent selected from H⁺; Li⁺; Na⁺; K⁺; Rb⁺; Cs⁺; NH₄ ⁺; Mg⁺²; Ca⁺²; Sr⁺²; Be⁺²; Ba⁺²; Y⁺³; La⁺³; Ce⁺³; Ce⁺⁴; Nd⁺³; Pr⁺³; Sc⁺³; Sm⁺³; Eu⁺³; Eu⁺²; Gd⁺³; Tb⁺³; Dy⁺³; Ho⁺³; Er⁺³; Tm⁺³; Yb⁺³; Lu⁺³; Ti⁺⁴; Zr⁺⁴; Ti⁺³; Hf⁺⁴; Nb⁺⁵; Ta⁺⁵; Nb⁺⁴; Ta⁺⁴; V⁺⁵; V⁺⁴; V⁺³; Mo⁺⁶; W⁺⁶; Mo⁺⁵; W⁺⁵; Mo⁺⁴; W⁺⁴; Cr⁺³; Mn⁺²; Mn⁺³; Mn⁺⁴; Fe⁺²; Fe⁺³; Co⁺²; Co⁺³; Ni⁺²; Ni⁺³; Ni⁺⁴; Ru⁺²; Ru⁺³; Ru⁺⁴; Rh⁺³; Ir⁺³; Rh⁺²; Ir⁺²; Pd⁺⁴; Pt⁺⁴; Pd⁺²; Pt⁺²; Os⁺⁴; Cu⁺; Cu⁺²; Cu⁺³; Ag⁺; Ag⁺²; Ag³; Au⁺; Au⁺²; Au⁺³; Zn⁺²; Cd⁺²; Hg⁺; Hg⁺²; Al⁺³; Ga⁺³; Ga⁺; In⁺³; In⁺; Tl⁺³; Tl⁺; Ge⁺⁴; Ge⁺²; Sn⁺⁴; Sn⁺²; Pb⁺⁴; Pb⁺²; Sb⁺³; Sb⁺⁵; As⁺³; As⁺⁵; Bi⁺³; Bi⁺⁵; organic compounds containing at least one N⁺ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one arsonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site;

organic compounds containing at least one selenonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR⁴ ⁺, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.

105. The method of claim 104 wherein the cationic solubility control agent is selected from H⁺; Li⁺; Na⁺; K⁺; Rb⁺; Cs⁺; NH₄ ⁺; Mg²; Ca⁺²; Sr⁺²; Y⁺³; La⁺³; Ce⁺³Ce⁺⁴; Nd⁺³; Pr⁺³; Sc⁺³; Sm⁺³; Eu⁺³; Eu⁺²; Gd⁺³; Tb⁺³; Dy⁺³; Ho⁺³; Er⁺³; Tm⁺³; Yb⁺³; Lu⁺³; Ti⁺⁴; Zr⁺⁴; Ti⁺³; Hf⁺⁴; Nb⁺⁵; Ta⁺⁵; Nb⁺⁴; Ta⁺⁴; Mo⁺⁶; W⁺⁶; Mo⁺⁵; W⁺⁵; Mo⁺⁴; W⁺⁴; Mn⁺²; Mn⁺³; Mn⁺⁴; Fe⁺²; Fe⁺³; Co⁺²; Co⁺³; Ru⁺²; Ru⁺³; Ru⁺⁴; Rh⁺³; Ir⁺³; Rh⁺²; Ir⁺²; Pd⁺⁴; Pt⁺⁴; Pd⁺²; Pt⁺²; Cu⁺; Cu⁺²; Cu⁺³; Ag⁺; Ag⁺²; Ag⁺³; Au⁺; Au⁺²; Au⁺³; Zn⁺²; Al⁺³; Ga⁺³; Ga⁺; In⁺³; In⁺; Ge⁺⁴; Ge⁺²; Sn⁺⁴; Sn⁺²; Sb⁺³; Sb⁺⁵; Bi⁺³; Bi⁺⁵; organic compounds containing at least one N⁺ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR⁴ ⁺, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.

106. The method of claim 103 wherein the solubility control agent is the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions, chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, vanadates, or combinations thereof.

107. The method of claim 103 wherein the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, or combinations thereof.

108. The method of claim 100 wherein the manganese/valence stabilizer complex is adsorbed onto, into, or mixed with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof.

109. The method of claim 91 wherein the pigment is colored.

110. The method of claim 91 wherein the pigment exhibits a color change between manganese oxidation states.

111. The method of claim 91 wherein the pigment is light-fast.

112. The method of claim 91 wherein the substrate is selected from metals, semimetals, semiconductors, composite materials with anisotropic electrical conductivity, or materials in a conductive or dielectric medium.

113. The method of claim 91 further comprising surface treating the substrate before applying the pigment.

114. The method of claim 91 further comprising applying a coating to the substrate before applying the pigment.

115. The method of claim 91 further comprising applying a coating concurrently with applying the pigment.

116. The method of claim 91 further comprising applying a coating to the substrate, the coating selected from organic coatings, inorganic coatings, or combinations thereof.

117. The method of claim 116 wherein the coating is the organic coating selected from alkyd-type primers, acrylic primers, oil-based primers, polyester primers, epoxy primers, conductive primers, organic sol-gels, ketimine coatings, polyvinyl coatings, acrylic thermoplastics, asphaltic and coal tar thermoplastics, polyamide thermoplastics, polyethylene dispersion thermoplastics, fluorocarbon thermoplastics, chlorocarbon thermoplastics, silicone thermosets, polyurethane thermosets, polyester thermosets, epoxy-amine thermosets, epoxy-amide thermosets, epoxy-ester thermosets, epoxy-coal tar thermosets, furane thermosets, phenolic thermosets, butadiene styrene elastomers, chlorinated rubber elastomers, polysulfonated elastomers, neoprene elastomers, or combinations thereof.

118. The method of claim 116 wherein the coating is the inorganic coating selected from low temperature enamels, low temperature glass frits, carbonaceous coatings, zeolites, inorganic sol-gels, or combinations thereof.

119. A corrosion-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex, wherein the manganese/valence stabilizer complex is sparingly soluble, exhibits low solubility, or is insoluble in water at about 25° C. and about 760 Torr.

120. A method of making a corrosion-inhibiting pigment comprising:

providing a solvent;

providing a manganese source in the solvent forming a manganese solution;

providing a valence stabilizer; and

combining the manganese source and the valence stabilizer to form a manganese/valence stabilizer complex, wherein the manganese/valence stabilizer complex is sparingly soluble in water at about 25° C. and about 760 Torr.

121. A method of making a corrosion-inhibiting pigment comprising:

providing a manganese source;

providing a valence stabilizer; and

heating the manganese source and the valence stabilizer in an oxidizing environment to form a pigment containing trivalent or tetravalent manganese, wherein the trivalent manganese or tetravalent manganese compound exhibits low solubility or insolubility in water at about 25° C. and about 760 Torr.

122. A method for treating a surface for corrosion resistance, comprising:

providing a substrate to be coated; and

applying a manganese-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex, wherein the manganese/valence stabilizer complex is sparingly soluble in water at about 25° C. and about 760 Torr.

123. A method for treating a surface for corrosion resistance, comprising:

providing a substrate to be coated; and

applying a manganese-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and oxygen combined to form a manganese compound wherein the manganese/valence stabilizer complex exhibits low solubility or insolubility in water at about 25° C. and about 760 Torr.