USOO7789958B2

(12) United States Patent (10) Patent No.: US 7,789,958 B2 Sturgill et al. (45) Date of Patent: *Sep. 7, 2010

(54) NON-TOXIC CORROSION-PROTECTION 4,159,207 A 6, 1979 NLSS PGMENTS BASED ON MANGANESE 4,169,902 A 10/1979 De Long 4,285,726 A * 8/1981 Hund et al...... 106.1405 (75) Inventors: Jeffrey A. Sturgill, Fairborn, OH (US); 4,340.430 A 7, 1982 N. Andrew Wells Phelps, Kettering, OH - I W (US); Joseph T. Swartzbaugh, Clayton, 4,349,671 A 9/1982 Iqbal et al. OH (US) 4,366,312 A 12/1982 Iqbal 4,367,333 A 1/1983 Iqbal (73) Assignee: University of Dayton, Dayton, OH (US) 4.385,174. A 5/1983 Iqbal et al. (*) Notice: Subject to any disclaimer, the term of this 4,388,118 A 6/1983 Eppler patent is extended or adjusted under 35 4,388,160 A 6/1983 Rynne U.S.C. 154(b) by 0 days. 4.417,007 A 1 1/1983 Salensky et al. 4.417,008 A 1 1/1983 Salensky et al. This patent is Subject to a terminal dis- 4.420,340 A 12/1983 Mohr et al. claimer. 4,469,521 A 9/1984 Salensky (21) Appl. No.: 11/619,761 (22) Filed: Jan. 4, 2007 (Continued) (65) Prior Publication Data FOREIGN PATENT DOCUMENTS US 2007/O149673 A1 Jun. 28, 2007 BE 893.676 10, 1982 Related U.S. Application Data (62) Division of application No. 10/341,435, filed on Jan. 13, 2003, now abandoned. (Continued) (51) Int. Cl. OTHER PUBLICATIONS 4. fe 3.08: Derwent abstract for DE 2625401. (52) U.S. Cl...... 106/499; 106/436; 106/419; (Continued) 106/450; 106/453; 106/455; 106/456; 106/479; 106/480; 106/481; 106/1405; 106/1433; Primary Examiner—C. Melissa Koslow 106/1439; 106/1444; 106/1445; 524/413 (74) Attorney, Agent, or Firm-Dinsmore & Shohl LLP (58) Field of Classification Search ...... 524/413; 106/499,436,419,450,453,455,456,479, (7) ABSTRACT 106/480, 481, 14.05, 14.33, 14.39, 14.44, See application file for complete search history.106/1445 Corrosion-inhibiting------pigments based on manganese are described that contain a trivalent or tetravalent manganese/ (56) References Cited Valence stabilizer complex. An inorganic or organic material is used to stabilize the trivalent or tetravalent manganese ion U.S. PATENT DOCUMENTS to form a compound that is sparingly soluble, exhibits low 1,078,788 A 11/1913 Kaplan solubility, or is insoluble in water, depending upon the 1,216,451 A 2f1917 Holmes intended usage. Specific stabilizers are chosen to control the 2,396,327 A 3, 1946 Kvalnes et al. release rate of trivalent or tetravalent manganese during expo 2,649,383 A 8, 1953 Killian et al. sure to water and to tailor the compatibility of the powder 2,765,300 A 10, 1956 Hein et al. 2,791,513 A 5/1957 Siegel et al. when used as a pigment in a chosen binder system. Stabilizers 2,821,525 A 1, 1958 Waitkins et at. may also modify the processing and handling characteristics 3,055,833. A 9, 1962 Baltzer of the formed powders. Manganese/valence stabilizer com 3,440,254 A 4, 1969 Lenoir et al. binations are chosen based on the well-founded principles of 3,615,810 A 10/1971 Holznagel etal manganese coordination chemistry. Many manganese-va 3,725,102 A 4, 1973 Hummel etal lence stabilizer combinations are presented that can equal the 3,823,076 A 7, 1974 Rushmere performance of conventional hexavalent chromium or tet 3,832,205 A 8/1974 Lowery ravalent lead systems. It is emphasized that this abstract is 3,879,523 A * 4/1975 Miyata et al...... 423,250 provided to comply with the rules requiring an abstract which 4.012, 195 A 3, 1977 Noack will allow a searcher or other reader to quickly ascertain the 4,024,036 A 5, 1977 Nakamura et al. 4,028,372 A 6, 1977 Crounse et al. subject matter of the technical disclosure. It is submitted with 4,079,018 A 3, 1978 Noack the understanding that it will not be used to interpret or limit 4,096,090 A 6, 1978 Noack the scope or meaning of the claims. 37 C.F.R.S 1.72(b). 4,097484 A 6/1978 von Zelewsky et al. 4,109,176 A 8, 1978 Ernstausen et al. 19 Claims, No Drawings US 7,789,958 B2 Page 2

U.S. PATENT DOCUMENTS EP O368470 A1 5, 1990 EP O455.018 11, 1991 4,474,952. A 10/1984 Iqbal EP O458020 A1 11F1991 4,479,917 A 10/1984 Rothgery et al. EP O486778 B1 5, 1992 4,480,064 A 10/1984 Chopra et al. EP O488.430 A2 6, 1992 4,564,511 A 1, 1986 Desmond et al. EP OS23288 A1 1, 1993 4,612,014 A 9, 1986 Felix EP O634460 1, 1995 4,622,391 A 11, 1986 Lorenz et al. EP O675173 A2 10, 1995 4,628,082 A 12/1986 Lorenz et al. EP 1125989 A1 8, 2001 4,640,818 A 2f1987 Grierson et al. FR 2348257 4f1976 4,670,486 A 6, 1987 Cseh et al. GB 565951 12, 1944 4,673.445 A 6/1987 Tuttle, Jr. et al. GB 1064416 4f1967 4,788,411 A 11, 1988 Skinner GB 1117017 6, 1968 5,043,016 A 8/1991 Speer et al. GB 1123,859 8, 1968 5,066,695 A 11, 1991 Cseh et al. GB 1483.271 8, 1977 5,188,993 A 2f1993 Takahashi et al. GB 1528,547 10, 1978 5,226,956 A 7, 1993 Askew et al. GB 1532043 11, 1978 5,254,162 A 10/1993 Speer et al. GB 1534787 12/1978 5,298,092 A 3, 1994 Schriever GB 1546.536 5, 1979 5,322,560 A 6, 1994 DePue et al. GB 2101109 1, 1983 5.330,588 A 7/1994 Gulley GB 2103218 2, 1983 5,378,293 A 1/1995 Schriever GB 2113664 8, 1983 5,411,606 A 5, 1995 Schriever GB 21387.96 A 10, 1984 5,415,687 A 5, 1995 Schriever GB 2139206 A 11, 1984 5,468.307 A 11/1995 Schriever JP 611 13780 5, 1986 5,472,524 A 12/1995 Schriever JP 61.188470 8, 1986 5.487,949 A 1/1996 Schriever JP 276853 3, 1990 5,551,994. A 9, 1996 Schriever JP 3163169 7, 1991 5,587,059 A 12/1996 Yamoto et al. JP 699544 4f1994 5,672,329 A 9, 1997 Okada et al. JP 699545 4f1994 5,735,939 A 4, 1998 Glausch et al. JP 6126888 5, 1994 5,753,019 A 5/1998 Stephen et al. RU 472957 6, 1975 5,871,866 A * 2/1999 Barker et al...... 429,231.1 WO 930.5198 3, 1993 5,873,953 A 2/1999 Schriever WO 94.00619 1, 1994 6,004,476 A 12/1999 Verma et al. WO 951.4117 5, 1995 6,068,709 A 5/2000 Schapira et al. WO WO95/14117 * 5, 1995 6,074,464 A 6/2000 Eddinger et al. WO 9531093 11, 1995 6,193,815 B1 2/2001 Wada et al. WO 9605335 2, 1996 goes R. 39 stro et al. WO 962.1753 7, 1996 6,383,980 B1* 5/2002 Hagihara et al...... 502/.340 WO 9629448 9, 1996 6,416,868 B1 7/2002 Sullivan et al. WO 97.35928 A1 10, 1997 6.432,225 B1 8, 2002 Schriever WO 9848O75 10, 1998 6,472,079 B2 10/2002 Hayashi et al. WO 9851841 11, 1998 6,500,276 B1 12/2002 Minevski et al. WO O306O192 A 7, 2003 6,582,814 B2 6, 2003 Swiler et al. 2003/0221590 Al 12/2003 Sturgill et al. OTHER PUBLICATIONS 2003/0230363 Al 12/2003 Sturgill et al. 2003/0234063 Al 12/2003 Sturgill et al. Suresh et al., “Investigation of Manganese-Molybdenum 2004, OO11252 A1 1/2004 Sturgill et al. Diethyldithiocarbamate Complex As a Potential System for Solar 2004, OO1691.0 A1 1/2004 Phelps et al. Energy Conversion'. Int. J. Energy Res. 23, pp. 229-233, 1999.* 2004.0020568 A1 2/2004 Phelps et al. Abstract, Czech. 145, 575, Dobrovolny, J., “Monoazo lacquers', in 2004/O104377 A1 6/2004 Phelps et al. Chemical Abstracts, vol.78:137932k, 1973, p. 98. 2004/0231754 A1 1 1/2004 Phelps et al. Abstract, Czech. CS 221, 701, Muzik, F. et al., “AZo pigments', in Chemical Abstracts, vol. 104:20733k. FOREIGN PATENT DOCUMENTS Abstract, Paintindia 1968, 18(6), 17-23, 52 (Eng), Potnis, S.P. et al., "Metallized azo pigments. IV. Pigments based on o-aminophenol and BE 89.3677 10, 1982 8-hydroxyquinoline', in Chemical Abstracts, vol. 70:30021 v. 1969, DE 938147 1, 1956 p. 70 DE 1278644 9, 1968 Abstract, 1(1), 59-76 (Ger). Roueche, A., “Metal salts of 5,5'- DE 2533.958 2, 1977 methinebis(barbituric acid) derivatives, their application as pig DE 2625401 * 12, 1977 ments', in Chemical Abstracts, vol.94:104876x, 1981, p. 80. DE 2642049 3, 1978 Abstract, Japan. Kokai 76,128,332, Hoshino, M. et al., “Nontoxic DE 2642049 A1 5, 1979 anticorrosive pigments for resin coatings'. 42-Coatings, vol. DE 2936748 4f1981 86:74537c, 1977. DE 3309.194 A1 10, 1983 Abstract, Japan. Kokai 76,128,331, Hoshino, M. et al., Nontoxic DE 3712946 10, 1987 anticorrosive pigments for resin coatings, 42-Coatings, vol. DE 38244.54 1, 1990 86:74538d, 1977. DE 3935478 5, 1991 Abstract, Japan Kokai 76,08,316, Takagi et al., “Metal-complexed DE 4002564 8, 1991 azomethine pigments', 40-Dyes, vol. 84:181599e, 1976. DE 4131548 3, 1993 Abstract, Japan. Kokai Tokkyo Koho JP 60 23 451, Yamamoto DE 19714881 10, 1998 Symthetic Chemical Co., Ltd., “Napthalocyanine compounds', in EP O342152 11, 1989 Chemical Abstracts, vol. 103: 106304n, 1985, p. 74. US 7,789,958 B2 Page 3

Office Action of U.S. Appl. No. 1 1/832,704 dated Jun. 16, 2009. International Preliminary Examination Report pertaining to Interna Chemical Abstract Registry citation 100687-47-6, Mar. 8, 1986. tional application No. PCT/US2002/040084 dated May 5, 2004. Chemical Abstract Registry citation 256459-53-7, Feb. 22, 2000. his Acts,pertaining to related U.S. Appl. No. 1 1/832,704 dated F.A. Cotton, G. Wilkinson, Anorganische Chemie, 4th edition, pp. ar. Z3, 789-799, Wiley & Sons Inc., 1980. * cited by examiner US 7,789,958 B2 1. 2 NON-TOXC CORROSION-PROTECTION solubility calcium and magnesium chromates have also seen PGMENTS BASED ON MANGANESE Some limited use as pigments. The coating vehicles of these pigments include alkyd-type primers, acrylic primers, and CROSS REFERENCE TO RELATED elastomeric Sealants, among others. Some transition metal APPLICATIONS chromate pigments (e.g., complexed with copper, iron, man ganese, or cobalt) and organic chromate pigments (e.g., This application is a divisional of U.S. patent application bound with nitrogenous compounds Such as guanidinium) Ser. No. 10/341,435 filed Jan. 13, 2003 NON-TOXIC COR have been used in protective coating systems. Barium or lead ROSION-PROTECTION PIGMENTS BASED ON A MAN chromates have also been used as corrosion inhibitors, as well GANESE (now abandoned). 10 as colorants. Variations in chromate speciation (i.e., what the This application is related to commonly assigned U.S. chromate ions are bound to) will result in significant differ patent application Ser. No. 10/341,556 NON-TOXIC COR ences in protection when used as corrosion-inhibiting pig ROSION-PROTECTION PIGMENTS BASED ON PER ments, due to differences in chromate solubility. MANGANATE AND MANGANATE, filed Jan. 13, 2003 by A clear correlation between performance and solubility of Sturgill et al., the disclosure of which is incorporated herein 15 chromate pigments has been shown. However, oxidizing by reference (now abandoned). chromates can be dangerous to use as corrosion inhibitors if they are not delivered in Sufficient quantity in a timely manner BACKGROUND OF THE INVENTION to the location of a coating breach. The chromate composition was far more important to the corrosion inhibiting perfor This invention relates generally to compositions and meth mance of the primer film than the organic coating composi ods for the formation of protective, corrosion-inhibiting pig tion. ments without the use of chromium in the hexavalent oxida A principle use of zinc and strontium chromate pigments is tion state or lead in the tetravalent oxidation state. More in wash- or etch-primer formulations for aluminum protec particularly, this invention relates to non-toxic, corrosion tion. Wash- or etch-primers, which have been used since the inhibiting pigments based on trivalent and tetravalent man 25 1940s, represent one of the harshest application conditions ganese and methods of making and using the same. for chromate pigments. Wash-primers are applied to metal Inhibiting the initiation, growth, and extent of corrosion is Surfaces under acidic conditions where the primer is cured as a significant part of component and systems design for the a corrosion inhibiting film. Chromate pigment powders dis Successful long-term use of metal objects. Uniform physical persed in an alcohol/resin base mixture are combined with an performance and safety margins of a part, a component, oran 30 aqueous phosphoric acid diluent solution. The acid roughens entire system can be compromised by corrosion. Aluminum, the metal Surface and initiates cross-linking of the resin to Zinc, iron, magnesium, titanium and their alloys tend to cor form a pigment-filled polymeric film. The chromate pigment rode rapidly in the presence of water due to their low oxida may also be dispersed in other carriers that are not as harsh as tion-reduction (redox) potentials. The high strength 2000 and the wash primer. However, if a corrosion-inhibiting pigment 7000 series of aluminum alloys are used extensively in air 35 can Survive the harsh conditions of acid diluent, then it can craft and are very sensitive to corrosive attack. Materials such usually be successfully incorporated within other paint, poly as steels and carbon fibers with higher redox potentials will meric, or barrier film systems for corrosion inhibition. form a galvanic couple in water and promote corrosive attack An important use of chromate pigments is in coil coating when located near light metal alloys Such as aluminum. formulations for steel, zinc-coated Steel, or aluminum sheet A bare metal Surface or one that has been conversion 40 stock. Coil coatings can represent a challenging application coated, phosphated, sealed, rinsed, or otherwise treated will environment for pigments in that cure temperatures for these be protected by the application of a primer paint with a cor paints can exceed 100 C. Corrosion-inhibiting pigments for rosion inhibiting pigment. As used herein, the term "pigment' these applications must exhibit both throwing power to means chemically active compounds with the ability to inhibit corrosion and be thermally stable at elevated tempera inhibit corrosion at a distance, rather than simple colorants or 45 tures when incorporated into the paint. opacifiers. Oxidative compounds that are effective as corro Lead chromate pigments of various compositions are sion inhibitors tend to be highly colored and/or opaque. An mostly used as colorants, although they are also used for effective corrosion inhibiting pigment has throwing power corrosion protection, albeit often for different applications and can protect exposed base metal in a scratch or flaw by than Zinc or strontium chromates. This is necessitated by the oxidizing and passivating it at a distance during aqueous 50 much lower solubility of lead chromate in comparison to corrosion when dispersed in a Suitable carrier phase. These these other chromates. The dark yellow lead chromate (Pb compounds are usually solids or liquids that are typically CrO C.I. Pigment Yellow 34) exhibits a solubility of dispersed in a liquid carrier orbinder system Such as a paint or approximately 107 moles/liter Cr', whereas the darker wash. These compounds may also be used to help inhibit basic lead chromate (PbCrO.PbO, C.I. Pigment Orange 21) corrosion without a significant liquid carrier using an integral 55 exhibits slightly lower solubility in water. In addition, lead binder and/or a low-volatile application method. Barrier layer chromate can be combined with other lead compounds to formers such as Sol-gel coatings or polymeric films are also alter the spectral or solubility characteristics. For example, used, but they tend to have no inherent oxidizing character the lemon yellow lead silicochromate (PbCrO.PbSiO) and and no appreciable throwing power and fail to protect the reddish lead molybdate-chromate (PbCrO.PbMoO C.I. metal surface when the film is breached. 60 Pigment Red 104) are representative examples. Note: This Pigments that contain hexavalent chromium (CrVI) com same situation exists for Zinc chromate pigments such as pounds are the de facto standard for high-performance cor ZnCrO, ZnCrO.Zn(OH), and ZnCrO(OH).Zn(OH), rosion inhibiting paints and coatings for metal protection and wherein increased basicity leads to lowering of the solubil are a typical corrosion inhibitor used to protect aluminum, ity. Zinc, magnesium, iron, titanium, copper and their alloys. Zinc 65 While lead chromate can be used in some of the same (C.I. Pigment Yellow 36) and strontium (C.I. Pigment Yellow coating vehicles as Zinc or strontium chromate (i.e., alkyd 32) chromate pigments are typically used, although higher type primers), the much lower solubility of lead chromate US 7,789,958 B2 3 4 permits its use in binder systems for which Zinc or strontium ings that contain these materials can effectively inhibit cor chromate would be unsuitable. For example, lead chromate is rosion as barrier films until the coating is breached, as by a often used in oil-based paints (i.e., linseed oil) wherein scratch or other flaw. Films or coatings that do not contain greater than 75% by weight of the paint System is pigment. oxidizing species can actually enhance corrosion on a Surface The mechanistic action of the divalent leadion present in the after failure due to the effects of crevice corrosion. lead chromate pigments is discussed below. Manganese is one non-toxic, non-regulated metal which Pigments that contain tetravalent lead (Pb|V) are also used has been considered as a chromium or lead replacement. extensively in coatings for metal protection, especially for Manganese (like chromium or lead) exhibits more than one steels and cast irons. The most notable PblV pigment is red oxidation state (Mn", Mn, and Mn"). In addition, the lead (PbO, C.I. Pigment Red 105). Red lead is composi 10 oxidation-reduction potential is comparable to that of CrVI or tionally equivalent to lead plumbate (Pb),(PbO)). PblV in acidic solutions. For example, in acid solution: 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 107 moles/liter Pb" 15 (Glasstone, J. Chem. Soc. 121: 1456-69, 1922), implying an extremely low release rate of Pb|V. Red lead is used primarily in alkyd-type primers as well as oil-based paints such as those containing linseed oil. Calcium plumbate (CalPbO, CaldioxTM) is another rep The MiniV and MnIII ions are very good oxidizing species resentative example of a corrosion-inhibiting pigment con with oxidation-reduction potentials of +1.65, V and +1.49, V taining Pb|V. Due to its higher solubility in comparison to red (at pH 0), respectively. The hydroxyl and oxygen liberated lead, calcium plumbate is most frequently used for applica from water when MnV or Mn is reduced will oxidize tions where a quicker release of oxidizing ions is necessary nearby bare metal. This results in a passivated metal surface if for protection, Such as on galvanized steel. Calcium plumbate 25 Sufficient oxygen is released. The potential required to reduce is most frequently used in alkyd-type or acrylic primers. tetravalent or trivalent manganese to divalent manganese is The use of hexavalent chromium or tetravalent lead pig only 0.29 or 0.13 volts greater than that needed to add three ments allows a broad range of service conditions to be electrons to reduce CrVI to trivalent chromium (CriII). addressed by tailoring the solubility of the pigment to the Although neither MnIV or MnIII match PbTV in terms of application needs. Very low solubility pigments, such as red 30 redox potential, neither is significantly lower and so compa lead, employ other corrosion-inhibiting mechanisms in addi rable passivation of metal is achieved. Minil is formed during tion to oxidative passivation. The divalent leadions present in corrosion inhibition by the oxidation of base metal in the presence of MnIV or MnIII and water. MnII is similar to CrII red lead (and even lead chromate) have been observed to form in that neither is particularly effective as redox-based corro “lead soaps' after long storage when the pigment is used in sion inhibitors. conjunction with oil paints, especially those comprised of 35 linseed oil. “Lead soaps' are reaction products between the A number of pigments using manganese have been alkaline divalent lead ions and the long-chain carboxylic reported in the literature over the years, but none approach the acids present (i.e., oleates, linoleates, linolenates, palmitates, general performance or utility of Pb|V- or CrVI-based pig and Stearates). This indicates that even though these pigments ments. For example, Manganese Violet is a colorant com exhibit low solubility in water, the constituent ions are still 40 posed of Mn pyrophosphate with no oxidizing characteris chemically active, but less than their more soluble cousins. tics. The divalent lead ions form insoluble compounds with cor A number of compounds have been described as corrosion rosive anions such as Sulfate, and low-solubility compounds inhibiting agents, including organic mercapto and thio com with other corrosive ions such as chloride, thereby effectively pounds, cyclic tetraaza compounds, aminophosphonic acid, removing them from the corroding system. For the heavier, 45 and triazinedithiols and triazinetrithiols. Other compounds more insoluble lead pigments such as red lead and basic lead have been described as corrosion inhibiting when complexed chromate, the inhibiting action is due to both the oxidative with manganese, typically in the divalent charge state. tetravalent lead or hexavalent chromium ions, and the ability Among these compounds are porphyrin derivatives, tetraaza of the divalent lead ions to capture (insolubilize) corrosive organic compounds, phosphoric and phosphonic acids, naph anions such as Sulfate. 50 thenates, amidosulfonic acids, and amino acids. However, the Significant efforts have been made in government and pigments formed from these compounds provide only limited industry to replace CrVI and PbTV with other metals for corrosion protection and do not approach the benefit derived corrosion-inhibiting applications due to toxicity, environ from the use of hexavalent chromium. mental, and regulatory considerations. An effective replace In addition, the formation of manganese-containing pig ment for hexavalent chromate or tetravalent lead pigment 55 ments in which the manganese is complexed with ligands needs to have throwing power for self-healing coating Such as hydrazones, —O bidentates, azomethines, phthalo breeches. Throwing power is the ability of a highly oxidized cyanines, azo and disazo complexes, N-S bidentates, ion, such as hexavalent chromium or tetravalent lead, to oxi oXimes, tetraaza complexes, porphyrins, 1,2-dithiolates, and dize and passivate the exposed bare metal in a Small scratch or semicarbazones, has also been described. However, these flaw. 60 compounds do not use tetravalent or trivalent manganese and A number of materials have been introduced as corrosion are not used for anticorrosive applications. inhibiting replacement pigments for tetravalent lead- or U.S. Pat. No. 6,416,868 to Sullivan, et al. describes the use hexavalent chromium-based compounds. Commercially of alkaline earth-manganese oxides as pigments, wherein the available corrosion inhibiting pigments including com alkaline earth is selected from Mg, Ca, Sr. and Ba. The pig pounds such as molybdates, phosphates, silicates, cyana 65 ments are described as being colorants and as resisting heat mides, and borates that have no inherent oxidizing character build-up due to infrared reflectance. Corrosion inhibiting have been used as alternatives to chromate pigments. Coat characteristics of these compositions are not discussed or US 7,789,958 B2 5 6 claimed. Additional manganese-containing colorants, frits, order to achieve a high degree of corrosion resistance, a and ceramic pigments with no discussed or claimed anticor MnIII-based or MnIV-based pigment must exhibit the follow rosive properties are identified in U.S. Pat. Nos. 4,159.207 to ing characteristics: Nuss, 3,832,205 to Lowery, and 5,254,162 to Speer, et al., and German Patent Nos. DE 4131548 and DE 4002564, both to 1) A corrosion inhibiting pigment must contain a Suitable Speer, et al. Source of oxidizing species. These species quickly oxidize U.S. Pat. No. 4,469,521 to Salensky describes a corrosion bare metal and form a protective surface if bare metal is inhibiting pigment formed by sintering manganomanganic exposed in a coating breach. oxide (MnO) with oxides of calcium, Zinc, barium, magne 2) A valence stabilizer for the trivalent or tetravalent manga sium, or strontium. 10 nese ion is necessary to ensure that the ion will not be reduced U.S. Pat. No. 4.388,118 to Eppler describes a corrosion too quickly to the divalent state when released into solution or inhibiting black pigment formed by calcining calcium or in the coating. The importance of stabilizing the manganese strontium oxides or carbonates with manganese oxides. The ion in its trivalent or tetravalent charge State was not previ formed calcium manganese oxide or strontium manganese ously recognized as critical to the corrosion inhibiting func oxide pigments have very low oil absorption and high tint 15 tion of a pigment. strength. 3) The MnIII or MnlV pigment powder must be a “sparingly German Patents Nos. 26 42 049, 28 15306, and 26.25 401 soluble”, “low solubility, or “insoluble' compound in water to Hund, et al. describe the use of calcined calcium/iron/ when dispersed in its binder-carrier system. If the pigment is aluminum/manganese oxides as corrosion-inhibiting pig too insoluble in a selected coating system that requires inhibi mentS. tor release, an insufficient amount of corrosion inhibitor will Manganese oxides themselves have been described as be delivered to a flaw. A poorly formed, incomplete oxide being constituents in corrosion-inhibiting formulations. For layer produced by a pigment of too low solubility for a given example, U.S. Pat. Nos. 4,417,007 and 4,417,008 to Salensky, binder-carrier system will not only fail to inhibit corrosion, et al. as well as Belgian Patent Nos. BE 893,677 to Chopra, et 25 but can promote crevice corrosion and result in locally al. and BE 893,676 to Salensky, et al. describe manganoman enhanced corrosion rates. ganic oxide (MnO) as a constituent in a solvent-based paint The reservoir of oxidizing ions can be quickly flushed formulation comprised of resin binders and additional away if the pigment is too soluble, and typical corrosion will extenders, fillers, and solvents. Manganese dioxide (MnO) is also described as an anticorrosive constituent within formu begin. Highly soluble pigments are also known to result in 30 osmotic blistering of paint films and coatings. Trivalent or lations in French Patent No. 2,348.257 to Zatmann and Ger tetravalent manganese pigments that are too soluble can also man Patent No. DE 3935 478 to Ortlepp. be responsible for osmotic blistering depending on the aque U.S. Pat. No. 4,788,411 to Skinner describes a paint com ous permeability the carrier film. position described to prevent corrosion of welds. This com position is described as being composed primarily of Zinc It is difficult to place specific solubility values to these 35 optimum “sparingly soluble'. “low solubility”, or dust, with manganomanganic oxide (MnO) and organic “insoluble' pigment materials because there appear to be binder included. The Zinc pigment is described as being espe several variables associated with what makes an optimum cially important for corrosion protection. anticorrosive pigment material (e.g., specific resin/binder To date, no truly effective replacements have been devel system in which it is placed). The particle size and particle oped for pigments based on CrVI or PbIV. Accordingly, the 40 shape has been observed to noticeably affect the solubility of need remains for improved corrosion-protective pigments “low solubility” pigments such as lead chromate (e.g., May composed of currently unregulated and/or nontoxic materials and Kolthoff, J. Phys. & Colloid Chem. 52: 836-54, 1948). which have an effectiveness, ease of application, and perfor The solubility of the candidate trivalent or tetravalent man mance comparable to current CrVI or Pb|V pigment formu ganese pigment must be matched to the hexavalent chromium lations, and for methods of making and using the same. 45 or tetravalent lead pigment that it is replacing (Table 1). Such as Zinc or strontium chromate, or calcium plumbate. If the SUMMARY OF THE INVENTION trivalent or tetravalent manganese pigment exhibits a solubil ity in water of between about 1x10' and about 1x10" moles This need is met by the present invention which represents per liter of trivalent or tetravalent manganese sparingly a significant improvement in the formulation of non-toxic 50 soluble, then appreciable corrosion inhibition will be pigments through the use of trivalent or tetravalent manga observed in the binder systems that typically incorporate zinc nese. Although the present invention is not limited to specific or strontium chromates (or calcium plumbate). Pigments that advantages or functionality, it is noted that the trivalent and/or incorporate stabilized trivalent or tetravalent manganese tetravalent manganese pigments of the present invention have compounds that fall outside of this particular range may also been demonstrated with accelerated corrosion testing to 55 exhibit some corrosion inhibition as Zinc or strontium chro retard corrosion to a higher degree than prior art manganese mate (or calcium plumbate) replacements. For example, pig pigments and other alternatives to CrVI- or PblV-based cor ments with solubilities as high as 1x10" moles per liter or as rosion inhibiting pigments. These pigments have been tested low as 1x10 moles per liter of trivalent or tetravalent man to inhibit corrosion to the same degree as Zinc, strontium, and ganese at Standard temperature and pressure (about 25° C. lead chromate-based CrVI pigments, as well as red lead or 60 and about 760 Torr) will exhibit some corrosion resistance in calcium plumbate Pb IV pigments. The raw materials are not binder systems that currently incorporate Zinc or strontium exotic, are relatively inexpensive, and do not require compli chromate (or lead plumbate), although not as great as those cated synthesis methods. compounds which fall within the optimum solubility range. A The present invention utilizes “valency stabilization of the solubility range from 1x10 to 1x10 moles per liter triva trivalent or tetravalent manganese ion in the as-formed pig 65 lent or tetravalent manganese low solubility is desirable for ments to achieve corrosion resistance comparable to the more manganese pigments to inhibit corrosion in binder systems soluble chromate-based CrVI pigments. More specifically, in where lead chromate pigments are currently used. Pigments US 7,789,958 B2 7 8 that incorporate trivalent or tetravalent manganese that fall 6) The manganese/valence stabilizer complex can optionally slightly outside of this range may also inhibit corrosion as exhibit a color change between the trivalent or tetravalent and lead chromate replacements. For example, pigments with divalent manganese oxidation states. This color change can solubilities as high as 1x10 moles per liter or as low as act as a metric to determine when the “throwing power 1x10 moles per liter of trivalent or tetravalent manganese at associated with the pigments is no longer available, and when standard temperature and pressure (about 25° C. and about the paint system in which it is contained needs to be replaced. 760 Torr) insoluble will exhibit some corrosion resistance in For this reason, it is also optionally important that the color of binder Systems that currently incorporate lead chromate, these pigments that exhibit a color change between divalent although not as great as those compounds which fall within and trivalent or tetravalent oxidation states that is light-fast 10 (i.e., not changed by strong light). the optimum solubility range. Lastly, any trivalent or tetrava The effectiveness of an oxidizing species is a function of its lent manganese pigment that exhibits a solubility lower than individual oxidation-reduction potential, and more highly 1x10, but higher than 1x10'7(based on red lead solubility) oxidized species exhibit greater corrosion protection, moles per liter of trivalent or tetravalent manganese at stan although lower stability. A stabilizer is necessary to provide a dard temperature and pressure (about 25° C. and about 760 15 timed release of the inhibitor ion, as well as being needed to Torr) will exhibit some corrosion resistance in binder systems ensure that the oxidative strength will not be reduced too that currently incorporate red lead. Under special conditions rapidly. Thus, a valence stabilizer is required for the trivalent (i.e., very carefully controlled particle sizes), trivalent or tet or tetravalent manganese ion because of its reactivity and to produce controlled trivalent or tetravalent manganese solu ravalent manganese compounds with solubilities as high as bilities. The corrosion resistance of a number of aluminum 1x107 moles per liter trivalent or tetravalent manganese can alloys as tested using both ASTMB-117 and ASTMG-85 has be used as red lead replacements. The solubility characteris been enhanced through the use of stabilized trivalent and/or tics of the trivalent or tetravalent manganese in the pigment tetravalent manganese pigments. Not only do these optimized can be controlled through the use of valence stabilizer mate pigments retard corrosion to a higher degree than other prior rials that form compounds that fall within the desired solu art manganese pigments, but their corrosion resistance is bility ranges. A “controlled release' of trivalent or tetravalent 25 comparable to that of hexavalent chromium or tetravalent manganese can thus be achieved similar to the “timed lead systems. release' of hexavalent chromium or tetravalent lead in the In one aspect, the invention comprises a mechanistic and chemical approach to the production of corrosion-inhibiting “state-of-the-art” systems. pigments using trivalent or tetravalent manganese. This 30 approach uses stabilizer materials which form compounds TABLE 1. with trivalent or tetravalent manganese that match the Solubility Ranges for Trivalent and/or Tetravalent Manganese observed solubilities of hexavalent chromium or tetravalent Replacements for Hexavalent Chromium or lead pigments currently in use (see Table 1). The solubility Tetravalent Lead Pigments ranges reported provide a release of trivalent or tetravalent manganese at a rate slow enough that most binder systems Optimum Solubility 35 will provide protection for an extended period oftime and fast Hexavalent Chromium or Range Acceptable Solubility enough to inhibit corrosion during conventional accelerated Tetravalent Lead Pigment (moles/LMn' Range (moles/LMn' corrosion testing methods such as ASTM B-117 and G-85. to be Replaced and/or Mn.) and/or Mn.) Compounds that fall slightly outside of the solubility ranges Zinc Chromates (including 1 x 10' (upper) 1 x 10' (upper) shown in Table 1 may also provide Some corrosion-inhibiting basic forms) to to 40 activity under certain conditions and binder systems. How Strontium Chromates 1 x 10' (lower) 1 x 10 (lower) Calcium Plumbate ever, pigment compounds with aqueous solubilities far out Lead Chromates (including 1 x 10 (upper) 1 x 10 (upper) side of the target ranges are likely to be inefficient corrosion basic forms) to to inhibitors. Solubility control can be achieved using organic or Lead Molybdate-Chromate 1 x 108 (lower) 1 x 10' (lower) inorganic stabilizer materials. Lead Silicochromate 45 In an optional aspect, the invention is the achievement of Red Lead 1 x 10' (upper) 1 x 10' (upper) to to corrosion-resistant pigments using trivalent or tetravalent 1 x 107 (lower) 1 x 107 (lower) manganese by the use of Stabilizer materials which form compounds that exhibit electrostatic dipoles to form electro static barrier layers composed of ions such as hydronium 4) The “valence stabilizer” optionally helps establish an elec 50 (HO") or hydroxide (OH) in the presence of water. The trostatic barrier layer around the cation-stabilizer compound formation of these electrostatic barrier layers through the use in aqueous solutions. The nature and character of the electro of stabilizer materials can be achieved using organic or inor static double-layer Surrounding the cation-stabilizer com ganic materials. pound may be controlled and modified by careful selection of In another optional aspect, the invention is the achievement 55 of corrosion-resistant pigments using trivalent or tetravalent stabilizer species. In general, the electrostatic double layer manganese by the use of Stabilizer materials which form formed acts to protect the cation from premature reaction compounds that exhibition exchange behavior towards alkali with hydronium, hydroxide, and other ions in solution. The ions. The formation of this ion exchange behavior can be formation of electrostatic barrier layers also helps to impede achieved through the use of organic or inorganic materials. the passage of corrosive ions through the binder phase to the 60 In yet another optional aspect, the decomposition tempera metallic Surface. ture of the trivalent or tetravalent manganese/valence stabi 5) The trivalent or tetravalent manganese pigment material lizer complex upon which the pigment is based should be may also exhibition exchange behavior towards corrosion above 100° C. In addition, the melting temperature of the promoting ions, particularly alkali species. This optional con complex is typically above 50° C., although lower-melting sideration can be important because alkali ions are aggressive 65 complexes may have some applications. aqueous corrosion enhancers in alloys which contain metals In still another optional aspect, the manganese/valence Such as aluminum, magnesium, or Zinc. stabilizer complex upon which the pigment is based should US 7,789,958 B2 9 10 exhibit a color change between the trivalent or tetravalent and pigments. These include a manganese source, an oxidation divalent oxidation states. This allows for a visual metric of Source (if the precursor is a divalent manganese salt), a when the pigment has lost its “throwing power, and the valence stabilizer source, and optional additional solubility binder system within which it is contained must be replaced. control agents. Therefore, it is desirable that the color of these pigments be light-fast (unchanged by exposure to strong light). 1) Manganese Source These MnIII and MnIV compounds represent a substantial Manganese is a nontoxic, non-regulated replacement metal performance improvement over prior art related to pigment for chromium or lead that exhibits more than one oxidation alternatives used to replace CrVI-based and PblV-based cor state (MnII, MnIII, and MnIV). The oxidation reduction rosion inhibiting pigments. They also provide a capability to 10 potential for MnlII-MnII is comparable to that of the CrVI tailor the corrosion inhibiting pigment to the carrier system. CriII couple, and the oxidation-reduction potential for MnIV This allows current binder/resin systems used for chromates MnIII is comparable to the PbIV-PbII couple. The ionic radii or plumbates to be used for MnIII- or MiniV-based systems of MnlII (61 pm) and MnIV (54 pm) are slightly larger than without modification. Likewise, new binder/carrier/resin sys the CrVI ion (44 pm), and they will have a correspondingly tems with improved physical properties can be developed 15 without the restriction of compatibility with zinc, strontium, lower charge density (electrostatic field) perion as compared or lead chromate; or plumbate pigments. to hexavalent chromium. Conversely, both MnIII and MnIV The raw materials needed for the solutions used to form are smaller than PbIV (78 pm), and have a higher charge these coatings are relatively inexpensive. The pigments do not density (electrostatic field) per ion compared to tetravalent use exotic materials or require complicated synthesis meth lead. These factors are important in the selection and design ods. of trivalent or tetravalent manganese compounds that match Accordingly, it is an object of the present invention to or exceed the performance of hexavalent chromium or tet provide non-toxic, corrosion-protective pigments based on ravalent lead pigments. trivalent or tetravalent manganese and for methods of making Unlike most other high valence metal (HVM) systems, and using the same. These and other objects and advantages 25 trivalent and/or tetravalent manganese ions exhibit remark of the present invention will be more fully understood from able stability under many environmental conditions. The the following detailed description of the invention. It is noted numerous examples of manganese minerals that contain that the scope of the claims is defined by the recitations MnIII or MnIV are evidence of this stability (see Table 2 therein and not by the specific discussion of features and below). Trivalent or tetravalent manganese-containing min advantages set forth in the present description. 30 erals could conceptually be used as corrosion-inhibiting pig ments. (However, natural impurities contained therein would DETAILED DESCRIPTION OF THE INVENTION alter the compositions so that the pigment materials would exhibit altered solubility characteristics.) The trivalent or tet A. Starting Materials ravalent manganese minerals shown in Table 2 could be used Four general starting materials are used for the preparation 35 as precursors for the production of anticorrosive manganese of trivalent or tetravalent manganese corrosion-inhibiting 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 Approximate Manganese Mineral Composition Valence State(s) Crystal Structure Pyrolusite MnO2 +4 Tetragona Hausmannite MnO, +3+2 Tetragona Manganite MnO(OH) +3 Tetragona Ramsdellite MnO2 +4 Orthorhombic Bixbyite Mn2O3 +3 Cubic Groutite MnO(OH) +3 Orthorhombic Feitknechite MnO(OH) +3 Tetragona Akhtenskite MnO2 +4 Hexagona Buserite MnO2 +4 Unknown Nsutite Mn(O,OH), +4+3 Hexagona Hetaerolite ZnMn2O +3 Tetragona Marokite CaMn2O +3 Orthorhombic Hydrohetaerolite HZnMn2O +3+2 Tetragona Braunite Mn/SiO2 +3+2 Tetragona Psilomelane (aka (Ba.H2O)2MnsOo +4+3 Monoclinic Romanechite) Cryptomelane KMnsO16 +4+3 Monoclinic or Tetragona Manjiroite (KNa)MnO6 +4+3 Tetragona Lithiophorite (Al Li)MnO(OH), +4+3 Hexagona Chalcophanite (Zn,Fe,Mn)MnO, +4 Rhombohedral Hollandite (Ba.K.Na)Mn(O,OH)6 +4+3 Unknown Woodruffite (Zn,Mn)MnO, +4 Tetragona Neltnerite CaMnSiO2 +3 Tetragona Birnessite NaMn4O27 +4+3 Hexagona US 7,789,958 B2 11 12

TABLE 2-continued Naturally-Occurring Trivalent and/or Tetravalent Manganese-Containing Minerals Useful as Feedstock for Anticorrosive Manganese Pigment Production Approximate Manganese Mineral Composition Valence State(s) Crystal Structure Asbolane (NiCo),Mn(O,OH) +4+3 Hexagonal Todorokite (K.Ca,Na)(Mn,Al,Mg)6O2 +4+3 Monoclinic Vernadite (Mn, Fe,Ca,Na)(O,OH)2 +4+3 Hexagonal

a) Manganese Sources for “Sparingly Soluble' Pigments b) Manganese Sources for “Low Solubility” or “Insoluble' Zinc and strontium chromates, as well as calcium plum 15 Pigments bate, are “sparingly soluble' in water, and are typically Lead chromates are typically formed via precipitation from formed via precipitation from a liquid media (i.e., water), aqueous solution, while red lead pigments are produced by with Subsequent particle sizing and powderprocessing. Triva firing Pb|I oxide (PbO) in an oxidizing environment at lent or tetravalent manganese pigments to be used for the approximately 400° C. Trivalent or tetravalent manganese same applications as Zinc and strontium chromates, or cal compounds to be used as lead chromate or red lead replace cium plumbate, are produced in a similar fashion. This is ments can be formed in two ways: 1) precipitating a manga because the higher solubility requirements (1x10' to 1x10' nese compound from a liquid medium and then firing or moles/liter inhibitorion) for these pigments necessitate much calcining the resultant precipitate; or 2) calcining or firing a higher release rates of MnlII or MnV than can typically be 25 manganese-containing compound or mixture using insoluble achieved by calcined or “fired” materials. MnIII or MnIV precursors. The commonality between these two options is compounds that can achieve high solubilities and release rates firing, calcining, or otherwise heating a manganese-contain require special valence stabilizer and/or solubility control ing compound or mixture. The only manganese compounds Suitable as replacements for lead chromate or red lead pig agents. The easiest preparative method for these constituents ments (<1x10 moles/liter inhibitorion) are those produced is via precipitation processes. 30 by calcining or heating manganese compounds with or with Manganese precursors for "sparingly soluble' pigments out other additives. can be nearly any water, alcohol, or hydrocarbon soluble Soluble manganese sources for precipitation prior to cal manganese compound in which the manganese is in the diva cining, firing, or otherwise heating are similar to those lent, trivalent, tetravalent, or heptavalent oxidation state. 35 described above for “sparingly soluble' pigments. Insoluble Water-soluble precursors are typically used. Inorganic diva manganese-containing compounds useful as precursors lent manganese precursor compounds include, but are not include MnII, MnIII, MnIV, and some MnVII compounds. limited to, manganese nitrate, manganese Sulfate, manganese Insoluble divalent manganese compounds useful as precur perchlorate, manganese chloride, manganese fluoride, man sors include, but are not limited to: manganese oxide (man ganese bromide, manganese iodide, manganese bromate, 40 ganosite), manganese hydroxide (pyrochroite), manganese manganese chlorate, and complex fluorides such as manga carbonate (rhodochrosite), manganese silicate (rhodonite, nese fluosilicate, manganese fluotitanate, manganese fluozir tephroite, manganhumite, or manganjustite), manganese Sul conate, manganese fluoborate, and manganese fluoaluminate. fide (alabandite or hauerite), manganese phosphate (redding Organometallic divalent manganese precursor compounds ite or hureaulite), manganese oxalate, and manganese borate. include, but are not limited to, manganese formate, manga 45 Insoluble trivalent manganese or tetravalent manganese com nese acetate, manganese propionate, manganese butyrate, pounds suitable as precursors include manganese dioxide manganese Valerate, manganese benzoate, manganese glyco (MnO), manganomanganic oxide (MnO), manganese ses late, manganese lactate, manganese tartronate, manganese quioxide (Mn2O), lithiated manganese spinel (LiMn2O4), malate, manganese tartrate, manganese citrate, manganese and manganese III hydroxide (MnOOH). The Mn(II and benzenesulfonate, manganese thiocyanate, and manganese 50 MnIV containing minerals described in Table 1 are also use acetylacetonate. ful insoluble trivalent and tetravalent manganese precursors. MnIII and MnIV are capable of providing corrosion pro The manganese precursor for "sparingly soluble' pigments tection at a distance to a metal Surface in the presence of may also be a compound with manganese already in the coating flaws such as scrapes, Scratches, and holes because of trivalent or tetravalent oxidation state. A representative 55 their throwing power. The solubility of the MnIII or MnIV example is manganese III acetylacetonate. The manganese compound needs to be tailored to suit the needs of the pro precursor for "sparingly soluble pigments may be a com tection system and must be neither too high, nor too low in pound with the manganese in the heptavalent oxidation state that system. The protective system includes the binder phase, (permanganates). Heptavalent manganese precursors assorted modifiers, and under- and over-coatings. The system include, but are not limited to: potassium permanganate, 60 needs to be performance matched to its intended usage envi Sodium permanganate, lithium permanganate, ammonium ronment. Timely release and throwing power of the inhibitor permanganate, magnesium permanganate, calcium perman are critical to protective performance, but controlled tailoring ganate, strontium permanganate, barium permanganate, Zinc of these has not been taught in prior art. Likewise, the body of permanganate, ferric permanganate, nickel permanganate, systematic chemistry data required to control these properties copper permanganate, cobalt permanganate, cerium perman 65 has not been readily available in a form useful to help design ganate, lanthanum permanganate, yttrium permanganate, and coatings. The present invention outlines how to stabilize aluminum permanganate. MnIII and MnIV with a variety of materials so the MnIII and US 7,789,958 B2 13 14 MnIV may be adapted to a multitude of pigment applications 3) Valence Stabilizers with specific compatibility requirements. Manganese is effective as an oxidative corrosion inhibitor if it can be supplied in sufficient quantities in the trivalent 2) Oxidation Source and/or tetravalent charge-state when brought into contact If MnIII and/or MnlV pigment compounds are produced with unprotected bare metal. Corrosion resistance compa via precipitation, an oxidizing species will typically be rable to that of CrVI or PbTV can be achieved by the use of included in the synthesis solution if divalent manganese com MnIII and/or MnIV oxidizer ions in pigment compounds. pounds are used as precursors for MnIII and MnIV. Other Valence stabilizers are materials that, when assembled, wise, a post-precipitation oxidation step will be required. modify the rate of reduction and the solubility of the MnIII Additional amounts of oxidizer may be added to help control 10 and/or MnIV ions. Valence stabilization has not been previ and maintain a desired amount of MnIII/MnIV in the pigment ously recognized as an important consideration in the devel solution by reoxidizing MnIII/MnIV that has become opment of effective corrosion inhibiting pigments. Stabiliza reduced. The trivalent manganese ion is an exceptionally tion helps avoid reduction and premature conversion of the good oxidizing species with an oxidation-reduction potential ion to the divalent charge-state during compound formation, of +1.49, V at a pH of 0 for the MiniTI-Mn II couple in water, 15 carrier incorporation, application, and exposure to a corrosive and the tetravalent manganese ion is an even stronger oxidiz environment. Stabilizers control solubility, mobility, ion ing species, with a redox potential of +1.65 V under similar exchange, binder compatibility, and the degree of Surface conditions. Strong oxidizers are required because of the high wetting. The exact solubility of this compound may be modi potential of their redox reaction. The oxidizers may be gases, fied by species released into solution by the dissolving metal liquids, or solids. Solid oxidizers are typically used for this surface or by the subsequent addition of solubility control application due to ease of handling and reagent measurement. agents. A variety of inorganic and organic stabilizers are Other starting materials (manganese source and stabilizer available that can serve to control solubility. The stabilizer Source) will also frequently be solids. Liquid oxidizers may may also act as an ion-exchange host and/or trap for alkali or be used, but handling and accurate process metering have halide ions in Solution. proven difficult. Gaseous oxidizers may be the most cost 25 Valence stabilization is necessary for MnIII and MnIV due effective and chemically efficient on a large Scale, but are also to the reactivity of these ions with water. Unlike MnII, which the most problematic due to handling and venting concerns. can readily be solubilized in water, MnIII and MnIV ions Oxidizers Suited for the purpose of producing and main rapidly react with water, producing elemental oxygen. taining the manganese ionin the trivalentortetravalent charge Valence stabilization is particularly useful for the more state include but are not restricted to peroxides and peroxo 30 soluble MnIII and MnV compounds (i.e. >1x10 moles/ compounds (including Superoxides, persulfates, perborates, liter of inhibitor ion) where more rapid release rates of these pernitrates, perphosphates, percarbonates, persilicates, per ions are necessary. For example, manganese dioxide (MnO) aluminates, pertitanates, perZirconates, permolybdates, per is reported to exhibit a solubility in water between 2.4x10 tungstates, pervanadates, and organic peroxyacid deriva and 4.0x107 moles/liter Mn", depending upon pH (Swain, tives), oZone, hypochlorites, chlorates, perchlorates, nitrates, 35 et al., Anal. Chem. 47(7): 1135-7, 1975 and Savenko, nitrites, Vanadates, iodates, hypobromites, chlorites, bro Geokhimiya (3) pp. 416-9, 1985). Similarly, manganese ses mates, permanganates, periodates, and dissolved gases Such quioxide (MnO) is reported to exhibit a solubility in water as oxygen, fluorine, or chlorine. Inorganic and organic deriva between 3.3x10 and 5.1x10 moles/liter Mn, depending tives of these compounds may be used. Typical oxidizers for upon temperature (Ampelogova, et al., Radiokhimiya 31(4): this use are peroxides, persulfates, perbenzoates, periodates, 40 160-5, 1989). For these low solubility compounds, oxygen bromates, hypochlorites, gaseous dissolved oxygen, and even (O) is a satisfactory “valence stabilizer” to achieve the desired the oxygen content of air. In general, any inorganic, organic, solubilities and release rates. Specialized valence stabilizers or combination species with an oxidation potential of +1.0,V are necessary for MiniTI and MnIV compounds of solubilities or greater (at a pH of 1) will be capable of oxidizing divalent higher than 1x10 moles/liter Mn" or Mn". manganese to the trivalent or tetravalent oxidation state. 45 The need for “valence stabilization' of trivalent or tetrava Oxidized manganese may also be produced in solution by lent manganese for corrosion inhibition has only been indi electrolytic oxidation. However, this approach may not be rectly noted in the general corrosion literature as a synergistic economically feasible due to the energy costs associated with enhancement. Corrosion inhibition behavior of nitrogen-con electrolytic oxidation. Chemical oxidation, such as that taining organics such as aniline or pyridine has been reported described above, currently offers the best-value approach for 50 to be enhanced with the addition of manganese. The exact oxidizing manganese to the trivalent or tetravalent state. nature of this “synergistic enhancement' has never been It is also possible to produce a divalent manganese/valence adequately explained. These “synergistic mixtures of nitro stabilizer complex, and then apply an oxidizer to oxidize gen-containing organics and manganese have also been divalent manganese to trivalent or tetravalent manganese. described as being "oxygen-Scavengers', and the organics are This, however, is less typical because the percentage of triva 55 frequently observed to “chemisorb’ onto the substrate piece lent or tetravalent manganese will decrease from the outside being protected. to the interior of the pigment particle. This enhancement can be explained by the “valence stabi Oxygen (including the oxygen content of air) is the most lization” model of corrosion inhibition by trivalent or tetrava useful oxidizer source for the production of “low solubility” lent manganese outlined here. Nitrogen-containing organics or “insoluble trivalent or tetravalent manganese pigment 60 and manganese result in the formation of an organometallic compounds via calcining, firing, or otherwise heating pro complex where the central manganese ion can be stabilized in cesses. The control of temperature, partial pressure of oxy a higher oxidation state. The observed "oxygen-Scavenging gen, flowrate, and even particle size allows the oxidation state phenomenon associated with dissolved oxygen in aqueous of the manganese in the sintered particle to be divalent, triva solutions is easily explained by the oxidation of stabilized lent, or tetravalent. Other oxidizing gasses such as NO, SO, 65 divalent manganese to the trivalent or tetravalent state. “Spar chlorine, fluorine, or OZone can also be used, but these are less ingly soluble' MnIII or MnIV complexes containing these desirable due to their environmental impact. organics are responsible for the corrosion-inhibiting activity, US 7,789,958 B2 15 16 and these organics will appear to be "adsorbed' or “chemi or near this solubility range can serve as a valence stabilizer sorbed' from solution onto the metal piece being protected for trivalent or tetravalent manganese. The assembly of a due to precipitation. protective shell around the highly charged MnIII or MnIV The key to providing a useful source of trivalent or tetrava and its associated oxygen and hydroxyl species can help lent manganese at a metal Surface is the creation of a com control the rate at which the manganese is reduced and its pound in which the MiniTI or MnIV ion is shielded from oxygen is released. Proper selection of materials for forming premature reduction during and after pigment formation. The the protective shell will allow solubility tailoring of the entire formation of pigments with the proper release rate of MnIII or assembly to its intended application environment. Valence MnIV ions is problematic because of the instability of MnIII stabilizers described above may need some type of additional and Mn(V in solution. A valence stabilizer must assemble 10 solubility control to optimize the performance of the trivalent around MnIII or MnIV to form a compound in order to pro or tetravalent manganese-valence stabilizer compound. Addi duce the active corrosion-inhibiting component in a pigment. tional solubility control agents may be in the form of inor It is difficult to place specific solubility values to these opti ganic or organic compounds. Their use is optional rather than mum sparingly soluble pigments because of the wide range of a requirement for effective valence stabilization and solubil binder systems in which corrosion-inhibiting pigments are 15 ity control. used. Trivalent or tetravalent manganese-containing compounds In order to replace the Zinc chromates, strontium chromate, that are useful as replacements for lead chromate or red lead or calcium plumbate pigments, a MnDI- or MnIV-stabilized pigments require lower Solubilities. A typical formula for a compound with a solubility in water ofbetween about 1x10' red lead paint is: and about 1x10" moles per liter of trivalent or tetravalent manganese should exhibit appreciable corrosion inhibition when used as a primer pigment. This solubility range pro Red lead (PbO) 80 wt. Percent vides a release of trivalent or tetravalent manganese at a rate Linseed oil 18wt. Percent slow enough that protection will be provided for an extended Turpentine and liquid drier 2 wt. Percent period of time and fast enough to inhibit corrosion during 25 conventional accelerated corrosion testing methods such as ASTM B-117 and G-85 for coatings that contain these pig The majority of this paint system is pigment. If the pigment in ments. Manganese compounds that fall outside of this par this paint system exhibited excessive solubilities for this spe ticular solubility range may exhibit a small degree of corro cific application, the coating would quickly be exhausted, sion inhibition in the binder systems that currently use the 30 leaving limited protection for the underlying metal. Zinc or strontium chromate pigments. For example, compo An optimum solubility range from 1x10 to 1x10 moles sitions with solubilities as high as 1x10" moles per liter or as per liter trivalent or tetravalent manganese is desirable for low as 1x10 moles per liter of trivalent or tetravalent man manganese pigments to inhibit corrosion in the binder sys ganese will exhibit some corrosion resistance, although they tems that lead chromate pigments currently are used in. Pig will not be as effective as those compounds within the opti 35 ments that incorporate trivalent or tetravalent manganese that mum solubility range. A common MnIII compound (MnIII fall slightly outside of this range may also inhibit corrosion as acetylacetonate) is too soluble to provide effective corrosion lead chromate replacements. For example, pigments with inhibition if incorporated into a binder system such as a paint. solubilities as high as 1x10 moles per liter or as low as Other compounds, Such as MnO, as described in the prior 1x10 moles per liter of trivalent or tetravalent manganese at art, will not serve as effective corrosion inhibiting pigments in 40 standard temperature and pressure (about 25° C. and about the binder systems that currently use the zinc or strontium 760 Torr) will exhibit some corrosion resistance in binder chromate pigments because they are too insoluble. systems that currently incorporate lead chromate, although The needed solubility will be strongly dependent on the net not as great as those compounds which fall within the opti aqueous solubility of overlying paints and coatings and their mum solubility range. usage environment. For example, solubility tailoring would 45 be useful in a situation where a protected substrate is suddenly Any trivalent or tetravalent manganese pigment that exhib immersed in seawater, or where a rubber sealant allows only its a solubility lower than 1x10 moles per liter of trivalentor limited water penetration. Adequate corrosion protection tetravalent manganese at standard temperature and pressure could be achieved through the formation of a trivalent or (about 25°C. and about 760 Torr) will exhibit some corrosion tetravalent manganese pigment compound that exhibits a 50 resistance in binder systems that currently incorporate red higher solubility in water (e.g., 1x10" to 1x10 moles per lead. Under special conditions (i.e., very carefully controlled liter MnIII or MiniV). A rapid release of protective trivalent or particle sizes), trivalent or tetravalent manganese compounds tetravalent manganese ions would happen at the expense of with solubilities as high as 1x107 moles per liter trivalent or depleting the manganese quickly from the coating. Trivalent tetravalent manganese can be used as red lead replacements. or tetravalent manganese pigments of lower Solubilities (e.g., 55 As with the more soluble MnHI and MnIV compounds 5x10 to 1x10 moles per liter MnIII or Mn(V) may also be used as Zinc or strontium chromate replacements, changes in useful in Some situations (e.g., as paints in nearly pure deoxy pigment solubility can be achieved through the use of addi genated water). The number and range of compound solubili tional Solubility control agents. ties offered by valence stabilized MnIII and MnIV com Several variables are associated with making optimized pounds allows the development of protective coating systems 60 pigments. If the pigment is too insoluble for the specific with broad performance and application ranges. This feature application, then insufficient trivalent or tetravalent manga is not presently available even for CrVI based corrosion nese is available to inhibit corrosion. Low solubility com inhibiting pigments. pounds that do not provide a sufficient amount of oxidation Any material in the synthesis bath which complexes with quickly enough to a coating breach may produce an incom trivalent or tetravalent manganese (whether inorganic or 65 plete oxide layer and thus an ineffective barrier film. If the organic) and which results in the formation of a MnlII- or manganese pigment is too soluble, it will be washed away MnIV-containing compound that exhibits solubilities within quickly, and an incomplete thin oxide film will form that will US 7,789,958 B2 17 18 not provide long-term corrosion protection, or osmotic blis charge, have a natural electrostatic dipole, or can have an tering of the paint system may result. The formation of spotty induced dipole. However, these compounds do not normally or patchy oxides can promote localized crevice corrosion and act as corrosion inhibitors because they have not been opti can result in enhanced corrosion rates at the breach. mized for that purpose. The traditional chromate pigments are used not only in The melting point and decomposition temperature of the alkyd resin systems (e.g., DoD-P-15328D Wash Primers), but pigment material are important. Trivalent or tetravalent man also in acrylic systems (e.g., MIL-P-28577B Water-Borne ganese-valence stabilizer compounds that decompose below Acrylic Primers), and even in Sulfonated rubber sealants (e.g., about 100° C. limit both their useful lifetimes and range of MIL-PRF-81733D Sealing and Coating Compound). Tet use. The melting temperature should be above about 50° C. to ravalent lead pigments are typically used in either oil-based 10 ensure that the liquid phase does not form during normal (i.e., linseed oil) paint systems, although some are used in handling procedures. An additive may be needed for pig alkyd resin coatings. Fortunately, it is possible to tailor the ments with melting temperatures below about 50° C. Inert MnIII and/or MnlV valence stabilizer compound pigment Solid addendum materials need not have any inherent corro systems themselves to specific binder/solvent systems using Sion-inhibiting capability and are used to provide a base (Sup solubility (cohesion) parameters. Solubility parameters 15 port) that the pigment can absorb on or into. Oxides, phos define how well an inorganic or organometallic complex will phates, borates, silicates, and polymers are examples of disperse in a given resin/binder system. This represents a Support compounds that can be used. Low melting tempera radical departure from traditional paint systems, in which the ture pigments (below about 50° C.) can be used, but they paint systems are configured to specific pigments. require handling and processing different from higher melt The formation of an electrostatic double layer can be ing temperature pigments. Liquid-phase corrosion inhibitors important for the effectiveness of a corrosion inhibitor once it based on MnIII, MnIV, and CrVI pigments have been dem is released into solution during corrosion. There are differ onstrated to provide excellent performance as corrosion ences in anodic and cathodic polarization, Solubility, and the inhibitors in primer paint systems. saturated pH of aqueous solutions of various chromate or The corrosion-inhibiting pigments of the present invention plumbate pigments. The formation of an electrostatic double 25 can optionally exhibit a color change between oxidized spe layer around the pigment while in its carrier film will not be as cies and divalent species. The implications of these color important as when the species is in Solution. For this reason, changes from an applications standpoint are significant. the development of an electrostatic double layer around the Color changes in the pigment material in use can be used as a pigment is an optional consideration. For example, Zinc chro metric to determine when the pigment no longer exhibits mate pigment-filled paint does not exhibit electrochemical 30 corrosion-inhibiting action as a result of depleting the oxi inhibiting behavior. The carrier film typically behaves as a dized ion. Changes in hue of the pigment can be used to water impermeable barrier and will muffle the polar character determine how much service life remains for that pigment in of the pigment. The hexavalent chromium pigments SrCrO. terms of corrosion-inhibiting capacity. Valence based color and ZnCrO have very small barrier layers associated with change is an attribute that conventional chromate or plumbate them, but they are effective as corrosion-inhibiting pigments. 35 pigments do not exhibit. The color change associated with Optimized solubility for MnIII- or MnIV-valence stabilizer their redox reaction of chromate or plumbate pigments is compounds alone can result in corrosion resistance compa insignificant as the pigments are reduced and "depleted of rable to the state-of-the-art chromium pigments. The degree their corrosion-inhibitive capability. Thus, trivalent or tet of polarization exhibited by the Mini II or MnIV ions will be ravalent manganese/valence stabilizer combinations that less than the CrVI ion because of their larger ionic radius and 40 exhibit these color changes are Superior to chromium or lead lower charge-state, and they will not be as efficient informing in terms of providing an easily measured, easily observed electrostatic double layers in aqueous solution. The Valence metric to gauge remaining service life of the pigment. How stabilization of trivalent or tetravalent manganese should be ever, this color change should not be initiated by exposure to optimized to achieve the highest degree of efficiency in both strong light. Light-fast pigments are therefore desirable for solubility control and polar character, in order to further 45 these indicator pigments. enhance the corrosion resistance. The incorporation of the Valence stabilizer (inorganic or Conversely, because both the MiniTI and MnIV ions are organic) may optionally result in the formation of a Mini- or smaller than the PblV ion, the degree of polarization exhib MnIV-valence stabilizer compound that also exhibits ion ited by these ions will be greater than PblV, and they will be exchange behavior towards alkali ions. This is not a require more effective informing electrostatic double layers in aque 50 ment of the MnIII- or MnIV-valence stabilizer compound, ous solution. In order to replace PbIV pigments, a lower and pigments that do not exhibit this phenomenon have been degree of valence stabilization is therefore acceptable. successfully demonstrated to inhibit corrosive attack. How The nature and character of the “electrostatic double layer” ever, it is a desirable characteristic for enhanced corrosion Surrounding the trivalent or tetravalent manganese/valence resistance. Existing CrVI-based or Pb|V-based pigment sys stabilizer compound may be controlled and modified by care 55 tems do not exhibit this behavior to any significant degree. ful selection of organic or inorganic stabilizers. Characteris The design of suitable MnIII- or MnIV-valence stabilizer tics such as the electrical dipole moment and the shape/con compounds allows typical and less typical stabilizers to be formation (for steric effects) of the stabilizer were found to identified. The general classes of compounds described influence the performance of the corrosion-inhibiting pig below represent only a first approximation of whether a spe ment. These stabilizer ions establish a protective electrostatic 60 cific coordination compound will provide favorable or unfa shell around the cation-stabilizer compound and gather addi vorable properties in a MnlII- or MnIV-valence stabilizer tional layers of ions such as hydronium (HO") or hydroxide compound. Property tailoring can also take place through (OH) about them. The size of the electrostatic double layer is selection of specific anions or cations bound to the MnIII- or a function of the electrostatic potential at the compound Sur MnIV-valence stabilizer coordination compound. The face and is inversely proportional to the ionic strength of the 65 “physiology of inorganic stabilizers is simple because of the surrounding solution. An electrostatic double layer will likely limited number of atoms and structural arrangements form in aqueous solution for compounds that can carry a involved in their formation. The “physiology' of organic US 7,789,958 B2 19 20 stabilizers is not as simple. An organically stabilized manga anced against the desired electrical properties. The Mn(II ion nese compound may have one or more organic ligands that generally favors complexation either in the square pyramidal may have one or more bonding sites that can interact with the (coordination number 5) or octahedral (coordination number MnIII or MnIV ion/oxide cluster. The bonding groups can be 6) arrangements, although it will occasionally be found in a the same or different atoms or functional groups on an indi pentagonal bipyramid arrangement. The Mn(V ion almost vidual or a variety of ligands. An organic stabilizer ligand can exclusively favors complexation in the octahedral (coordina be modified in an unlimited number of ways to tailor its tion number 6) arrangement. Valence stabilizers (and Stabi physical behavior with respect to Such properties as chemical lizer combinations) should be selected with the goal of reactivity, Solubility, electrostatic and polar character, and achieving these coordinations. functional behavior. 10 Stabilizers can be designed that result in manganese com It is possible to fine tune the electronic and structural char pounds with the necessary physical, electrical, and chemical acteristics of a MnDII- or MnIV-valence stabilizer compound properties to perform as corrosion inhibitors with this infor further via Substituent groups on the coordinating ligand, mation. The nature of a particular valence stabilizer shell and/or by the selection of cations or anions to complete the Surrounding the manganese ion, or combination of Valence charge balance of the MnHI- or MnIV-valence stabilizer.com 15 stabilizers, can be further manipulated by the selection of pound. For example, some Substituent groups have large appropriate “shaping groups' and heteroatoms at the binding dipole moments associated with them, which will increase the site. Inorganic valence stabilizers are typically oxygen-con electrostatic barrier layers associated with the manganese/ taining coordinations. Therefore, manipulation of different valence stabilizer complexes. These include: ketones sized ionic complexes around the MnlII or MnIV ions is best (=C=O), thioketones (=C=S), amides (—C=O— controlled through adjustment of the heteroatoms (e.g., Mo, NR), thioamides ( C=S NR), nitriles or cyano W. Te, etc.) within these “polymerized oxygen-containing groups, (—CN), isocyanides (—NC), nitroso groups ionic complexes (ligands). (—N=O), thionitroso groups (-N=S), nitro groups For organic compounds, the physical geometry of the bind (—NO), azido groups (-N), cyanamide or cyanonitrene ing sites is important to the stability of the MnlII- or MnIV groups (=N-CN), cyanate groups (-O-CN), isocyanate 25 stabilizer compound. The influence of site geometry becomes groups (-N=C=O), thiocyanate groups (—S—CN), evident when the solvation shell of a Mn or MnV ion is isothiocyanate groups (-N=C=S), nitrosamine groups replaced by the ligand donor atoms as when pigments are (—N N=O), thionitrosamine groups (—N N=S), nitra formed. The number of available ligand binding sites should mine groups (=N-NO), thionitramine groups (=N- be at least equal to the standard coordination number of the NS), carbonylnitrene groups ( CO N), thiocarbonylni 30 MnIII or MnV ion. The balance between solvation of the trene groups (—CS N), Sulfenyl halides (—S X), ligand and MnIII and/or MnIV and their complexation where sulfoxides (—S—O), sulfones (—S=O), sulfinyl groups MnIII or MnIV is solvated by a specific ligand is critical in ( N=S=O), thiosulfinyl groups ( N=S—S), sulfenyl maintaining stability. MnIII- or MnIV-ligand attraction thiocyanato groups (—S S-CN), Sulfenyl cyanato groups increases with the number of available binding sites on the (—S O CN), sulfodiimine groups (—S—NH), sulfur 35 ligand. However, with an increasing number of binding sites, dihaloimido groups ( N=SX), sulfur oxide dihaloimido site-site repulsions will also increase, resulting in lower sta groups ( N=S=OX), aminosulfur oxide trihalide bility. groups (=N-S=OX), Sulfonyl azide groups (—S The number of binding sites available on the complexing =ON), sulfonyl thiocyanate groups ( S=OSCN), ligand is important to the resulting MnIII- or MnlV-stabiliz Sulfonyl cyanate groups (—S=OOCN). Sulfonyl cyanide 40 er's properties. Several ligands are required to effectively groups (—S=O)CN), halosulfonate groups (—S=O stabilize MnIII or MnIV if the chosen ligand has only one OX), phosphonyl thiocyanate groups ( P=OOHSCN), binding site. For example, six NH ligands are needed to phosphonyl cyanate groups ( P=OOHOCN), and phos octahedrally coordinate MnlII in a hexaaminemanganese phonyl cyanide groups ( Pi—OOHCN). In this way, the (III) compound because NH has only one binding site. Bulky characteristics of less typical coordinating ligands may be 45 ligands with only one binding site, like pyridine, can be adjusted so that the resultant MnIII- or MnIV-valence stabi sterically hindered from packing tightly around the ion and lizer compound does exhibit some degree of corrosion inhi will result in decreased compound stability. Conversely, mac bition. Conversely, the physical characteristics of typical rocyclic organic and polymeric inorganic ligands can have coordination compounds can be adjusted so that they are no many suitable binding sites. However, instability will result if longer Suitable as a corrosion inhibitor. 50 a MnDI or MnlV ion is not completely embraced by all of the Valence stabilizers can be either organic or inorganic com multiple macromolecular bonding sites on the ligand. For pounds. Manganese coordination chemistry, which has been example, if a macromolecule surrounding the MnHI or MnIV the subject of numerous scientific studies for almost 100 ion has an insufficient number of binding sites available for years, identifies chemical binding preferences, structure sta charge balance, then the MnlII- or MnIV-stabilizer com bility, and the physical properties of the resulting compounds. 55 pound will be much less stable than a macromolecule that Producing effective MnIII- and/or MnIV-valence stabilizer contains an adequate number of sites. compounds requires understanding the electrostatic and The stability of the MnIII- or MiniV-organic compound is structural influence of candidate species on the compound. strongly influenced by the charge, charge sign, and degree of The solubility of the valence stabilized MnIII- and/or MnIV polarizability of specific binding sites. Factors influencing compound scales roughly with the inverse of its diameter. The 60 compound stability include: 1) ion-pair interactions for MnIII and MnIV ions and their layer of negatively charged charged ligands and MnIII or MnlV; 2) ion-dipole and ion hydroxyl ions are very small, which results in a high degree of induced dipole interactions for neutral ligands; 3) hydrogen aqueous solubility. The field strength of the complex also bonding; and 4) the hard-soft acid-base (HSAB) rules con scales with the inverse of its physical diameter. Large com vention of coordination chemistry. HSAB rules help identify pounds with an optimal degree of Solubility will not neces 65 functional groups on ligands that might be effective as bind sarily be ideal with respect to the size of their electrostatic ing sites. Optimum binding for organic Valence stabilizers to double layer. The size of the ligand must therefore be bal MnIII or MnlV will be with ligands with hard bonding spe US 7,789,958 B2 21 22 cies such as those that contain oxygen or nitrogen. Certain the ability of that ligand to flex around the MnHI or MnIV ions coordination complexes of the soft base sulfur are also effec So as to coordinate it as a square pyramid or octahedral com tive for binding with MnIII or MnIV. HSAB rules can also plex. help identify groups that might provide a degree of polariza The physical, chemical, and electrostatic requirements for tion to the stabilizer because of their large dipole moments. the design of effective pigments based on MnIII- or MnIV The nature of bonding between the MnIII or MnIV ion/oxide stabilizer compounds result in lists of stabilizers that may be cluster and the stabilizer ligand can be altered by using a divided into wide band or narrow band stabilizer classes for substituent group to modify the stabilizer. Specific interac MnIII or MnIV, depending upon the application. Wide band tions between the ligand and MnIII or MnIV can be tailored valence stabilizers can be used under a wide variety of service by Substituent group selection coupled with altering the size 10 conditions (e.g., corroding specie, temperature, etc.) to achieve a high degree of corrosion resistance. Wide band or geometry of the complexing ligand. Some Substituent physical properties (stability, Solubility, and polarization) can groups, such as carbonyls (ketones, amides, ureas), nitro be achieved by both inorganic or organic valence stabilizers. groups, cyano groups, and azido groups have large dipole The desirable physical property of ion exchange can also be moments. The polarization of the Mn(II- or MnIV-stabilizer 15 achieved with both inorganic and organic coordination com can therefore be optimized via evaluation of the effect of pounds. “Narrow band valence stabilizers result in satisfac ligand type and Substituents. tory pigments only under limited applications. Table 3 lists Finally, the size of the valence stabilizer plays an important the wide and narrow band valence stabilizers for Mini and role in solubility control of the resultant MnIII- or MnIV MnIV depending upon the specific application. Valence stabilizer compound. As the ligand increases in size, The compounds listed here are general guides for the initial it becomes more difficult to keep it in solution, therefore selection of a coordination compound and do not represent a lowering the solubility. However, this must be balanced complete list. Tailoring Substituent groups and the selection against the fact that as ligands are increased in size, it also of cations oranions for charge balance can influence whether becomes more difficult to establish the necessary dipoles at a particular Mn(II- or MnIV-stabilizer compound will have the compound/water interface. The size of the ligand must 25 wide band or narrow band corrosion inhibiting characteris therefore be balanced against the desired electrical properties. tics. Both inorganic or organic valence stabilizers may form The addition (or Subtraction) of functional groups on organic compounds with the necessary physical properties of Stabil valence stabilizers can be used to modify the solubility of the ity, solubility, and polarization to be effective corrosion inhib formed Mn" or Mn"/valence stabilizer species. For iting pigments. example, the addition of Sulfonated groups (—SO) to 30 organic Valence stabilizers will significantly increase the TABLE 3 solubility in water. Other substituent groups that will increase Wide and Narrow Band Valence Stabilizers for Trivalent and or the solubility in water include: carboxyl groups (-CO), Tetravalent Manganese Replacements for Hexavalent Chronium or Tetravalent Lead Pigments hydroxyl groups (-OH), ester groups (—CO ), carbonyl 35 groups (=C=O), amine groups (-NH), nitrosamine Hexavalent Chromium or Narrow Band groups (—N N=O), carbonylnitrene groups ( CO N), Tetravalent Lead Pigment Wide Band Valence Valence Sulfoxide groups (=S=O), Sulfone groups (=S=O), to be Replaced Stabilizers Stabilizers sulfinyl groups ( N=S=O), sulfodiimines (—S=NHI), Zinc Chromates (including Inorganic: Inorganic: Sulfonyl halide groups (—S=OX), Sulfonamide groups 40 basic forms) Molybdates, tungstates, Bismuthates, (—S=O)NH), monohalosulfonamide groups (—S=O) Strontium Chromates vanadates, niobates, germanates, Calcium Plumbate tantalates, tellurates, arSenates NHX), dihalosulfonamide groups (—S=OMX), halosul periodates, iodates, fonate groups (—S=OOX), halosulfonate amide groups antimonates, stannates, (—N S=OX), aminosulfonate groups (—N S=O) Sulfates, polyphosphates OH), iminodisulfonate groups (—NISO), phosphonate 45 Organic: Organic: See Table 4 See Table 5 groups (-PO), phosphonamide groups (-PO.NH), Lead Chromates (including Inorganic: Inorganic: phosphondiamide groups (—PONH2), aminophosphonate basic forms) Oxygen, titanates, Carbonates groups (=N-POs), and iminodiphosphonate groups (-N Lead Molybdate-Chromate Zirconates, tantalates, IPOs). Conversely, the addition of nitro groups ( NO.), Lead Silicochromate aluminates, silicates, phosphates, borates perfluoroalkyl groups (—CF), perchloroalkyl groups 50 Organic: Organic: (—C,Cl), nitramine groups (-N-NO), thioketone Ole Ole groups (=C=S), Sulfenyl halide groups (—S X), and Sul Red Lead Inorganic: Inorganic: fur dihaloimide groups (-N=SX) to organic valence sta Oxygen, titanates, None Zirconates, tantalates, bilizers will decrease the solubility in water. In this way, the aluminates, silicates solubility characteristics of valence stabilizers can be “tai 55 Organic: Organic: lored to meet specific binder/resin needs. Ole Ole Valence stabilizers and combinations of stabilizers can be manipulated by the selection of “shaping groups' and het eroatoms positioned at the binding site. Saturated organic 3.a) Wide Band Inorganic Valence Stabilizers chains can form flexible ligands that wrap around MnIII- or 60 Wide band inorganic valence stabilizers are formed around MnIV- and can enhance their stability. Unsaturated organics the MnIII or MnlV ion by “polymerizing in synthesis solu typically have less freedom to bend and contort and are less tion. Inorganic wide band valence stabilizers for MnlII or likely to be a ligand that can wrap or fit around the MnIII or MnIV for “sparingly soluble' pigments include molybdates MnIV ions. Addition of Substituents onto an organic ligand (Mo', Mo', or Mo", for example Mn"MoC), and may further restrict its freedom to flex. For example, the 65 Mn"Mo.O.), tungstates (W. W.", or W", for attachment of a phenyl group onto an organic valence stabi example Mn"'WO' and Mn"WOz'), vana lizer that contains two or more binding sites will likely restrict dates (V" and V", for example Mn"VOs and US 7,789,958 B2 23 24 Mn"VOI), niobates (Nb" and Nb", for example materials will polymerize to form a mixed periodate/molyb Mn"NbO), tantalates (Ta' and Ta", for example date Valence stabilizer out of the pigment Solution. Mn"Ta-Oss'), tellurates (Te" and Te", for example The most notable valence stabilizer for low and insoluble Mn"TeOs'), periodates (I'7, for example Mn"I MnIII and MnIV pigments is oxygen (O), as evidenced by the Os'), iodates (I", for example Mn"I.Ols'), anti natural stability of such compounds as MnO, MnO, monates (Sb" and Sb'), stannates (Sn"), sulfates (S", such Mn2O and MnOOH, all of which contain MnIII and/or as manganese spinels [Mn(SO4)2'), and polyphosphates MnIV ions. In instances where oxygen is used as a valence (P", for example MnPO’ and MnPO'). Many stabilizer for Min or MnV, differences in addendum cat of these inorganics form octahedral and square pyramidal ions (i.e., Ca" in CaMnO, or Zn' in ZnMnO) are heteropolymetallate structures on precipitation from Solu 10 observed to alter the solubility of the formed compound, and tion. For example, tellurate ions begin to polymerize near pH its performance as a corrosion inhibitor in a given binder 5 in water and will complex with MnIII or MnlV ions in basic system. This is discussed under Section 4 describing Addi solution pHs. Therefore, as the pH is raised in the pigment tional Solubility Control Agents. synthesis bath, the tellurate ion polymerizes to polymorphs, Additional wide band valence stabilizers for Min or which then complex the MnlII or MnIV ion. 15 MnIV for “low solubility” or “insoluble' pigments include The general structural aspects of heteropolymetallates are silicates (Si", for example Mn, SiO'), borates (B", well understood, and the stability of heteropolymetallates as for example Mn"B.O.), phosphates (P", for example a function of composition and structure is also well-charac Mn", PO), titanates (Ti"), zirconates (Zr"), and alumi terized. The relatively unstable MnIII or MnIV ions are pro nates (Al"). These compounds can also form octahedral or tected and stabilized within the surrounding octahedral and square pyramids, but have a higher tendency to form chain square pyramidal groups, although specific configurations of like structures during calcining or firing. Combinations of the heteropolymetallate anions differ from stabilizer to stabi these materials. Such as phosphosilicates, aluminosilicates, or lizer (i.e., from molybdate to periodate or iodate). The dimen borosilicates may also function as wide band Valence stabi sions of the octahedra and square pyramids are controlled by lizers for low and insoluble MnIII and MnIV compounds. 25 the size of the heteroatom (e.g., Mo, W, or Te) around which 3b) Wide Band Organic Valence Stabilizers they are assembled. A variety of organic compounds meet the criteria to be A MnIII or MnlV ion trapped by the precipitation of these typical wide band valence stabilizers for MnIII or MnIV. heteropolymetallates and its resulting “ion within a cage' These coordination ligands produce MnIII or MnIV valence structure can exhibit an even greater apparent Volume due to 30 stabilized compounds that fulfill the general requirements of the development of a large electrostatic double layer. This a MnDI or Mn(V pigment material. Organic compounds can will influence both the valence stabilization of the Min or be very effective manganese stabilizers and provide the great MnIV, as well as the solubility of the assembled compound. est degree of freedom in designing new manganese-stabilizer These compounds are reported to be excellent ion exchange compounds with new functionalities. More possible organic agents for alkali ions. This caging structure serves to lower 35 Valence stabilizer species exist than inorganic Valence stabi the solubility of the MnIII or MnIV because the chemical lizers because of the immense number of organic compounds elements typically associated with these valence stabilizers and functionalities from which to choose. Water-soluble pre (e.g., I, Te, Mo, or W) are all inherently less soluble in water cursors for the organic Valence Stabilizers are generally used than Mn. These materials can also establish oriented dipoles so that pigment synthesis can be carried out in aqueous solu with the interior Minor MnVion and forman electrostatic 40 tion. However, alcohol or hydrocarbon soluble species can double layer during aqueous corrosion. Finally, the elements also be used. associated with these valence stabilizers themselves can con The number of wide band (and narrow band) organic com tain high valence ions (i.e., V", Te", or Mo"), which will pounds that are acceptable as valence stabilizers for trivalent also serve somewhat in corrosion protection, although not to or tetravalent manganese is limited. Common organic com the degree of MnIII or MnIV (or CrVI), due to their lower 45 pounds such as alcohols, aldehydes, ketones, esters, ethers, redox potential. alkyl or aromatic halides, most carboxylic acids, anhydrides, Water-soluble precursors for these materials are generally phenols, Sulfonic acids, phosphonic acids, carbohydrates, used so that the synthesis can be carried out from aqueous waxes, fats, Sugars, and oils are not as effective as the struc solution. Many elements associated with these stabilizers tural types described in these Tables to stabilize the trivalent (e.g., Mo, W, or Te) do not typically form water-soluble 50 or tetravalent manganese ion. At best, Some of the organic compounds so the identification of Suitable precursors can be types described in these Tables may presently be used for difficult. other industrial applications, but their incorporation into cor Complex, partially-polymerized salts such as para- or rosion-inhibiting blends to stabilize trivalent or tetravalent meta-polymorphs for each compound may also be used as manganese has heretofore been unrecognized. precursors. These polymorphs typically exhibit slightly lower 55 The choice of Substituent functional groups on these gen solubilities in water than the simple salts. Peroxo-salts of eral classes of valence stabilizers will affect the physico these compounds, especially permolybdates, pertungstates, chemical properties of the MnIII- or MiniV-containing com and pervanadates may also be used as precursors. Formation pound and the corrosion resistance achieved using that of the chosen heteropolymetallates from precursors such as compound. For example, the addition of NH or =O sub the fluorides, chlorides, bromides, nitrates, and perchlorates 60 stituents increases the net polarization of the overall net MnIII (e.g., SnCl4 to form heterostannates and SbF5 to form het or MnIV/valence stabilizer compound, but will also increase eroantimonates) can be difficult, but may be acceptable in its water solubility. Careful molecular design of MnIII and certain circumstances. A valence stabilizer can be a cross MnIV compounds is necessary in order to achieve desired between two or more of the wide-band inorganic valence performance characteristics. stabilizers listed above. For example, a valence stabilizer 65 In general, the bonding atoms in typical organic valence composed of a periodate and a molybdate may be desirable in stabilizers are nitrogen, oxygen, or Sulfur. Bonding atoms Some situations. During the synthesis process, both of these Such as phosphorus, carbon, silicon, tin, arsenic, and anti US 7,789,958 B2 25 26 mony are much less desirable due to problems with valence dination with Mn" or Mn". These valence stabilizers all stability, toxicity, or solubility. Other stable coordinations serve to stabilize the Mn" or Mn" ions within a sparingly (like pentagonal bipyramidal) are known, even though these soluble complex that can exhibit a polar character in aqueous particular agents prefer octahedral or square pyramidal coor Solution.

TABLE 4 Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation NValence Stabilizer #1: NH, NH2R, NHR2, and NR where R Monoamines (N Monodentates) represents 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 Patoms. NValence Stabilizer #2: R—N-R-N-R", where R, R', and R" represent H Diamines (N. N. Bidentates) 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 Patoms. NValence Stabilizer #3: R N R' N R". N. R", where R, R', R", and R" Triamines (either N N Bidentates or N N represent H or any organic functional group Tridentates) wherein the number of carbon atoms ranges rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #4: R N R' N R". N. R" N R", where R, R', R", Tetramines (N. N. Bidentates, N. N. R", and R" represent H or any organic Tridentates, or N N 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 Patoms. NValence Stabilizer #5: R N R' N R". N. R" N R". N. R", where R, Pentamines (N. N. Bidentates, N-N R", R", R", R", and R" represent H or any Tridentates, or N N 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 Patoms. NValence Stabilizer #6: R N R' N R". N. R" N R". N. R" N R", Hexamines (N. N. Bidentates, N. N. where R, R', R", R", R", R", and R" Tridentates, N N Tetradentates, or N N represent H or any organic functional group Hexadentates) wherein the number of carbon atoms ranges rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #7: Five membered heterocyclic ring containing Five-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms, all of containing One, Two, Three, or Four which may or may not function as binding sites. Nitrogen Atoms wherein at least one Can include other ring systems bound to this Nitrogen Atom is a Binding Site (N heterocyclic ring, but they do not coordinate Monodentates or N N Bidentates) with the stabilized, high valence metal ion. Ring can also contain O, S, or Patoms. This 5 membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water-insolubilizing solubilizing groups attached. NValence Stabilizer #8: Six membered heterocyclic ring containing one, Six-Membered Heterocyclic Rings two, three, or four nitrogen atoms, all of which containing One, Two, Three, or Four may or may not function as binding sites. Can Nitrogen Atoms wherein at least one include other ring systems bound to this Nitrogen Atom is a Binding Site (N heterocyclic ring, but they do not coordinate Monodentates or N N Bidentates) with the stabilized, high valence metal ion. Ring can also contain O, S, or Patoms. This 6 membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water-insolubilizing solubilizing groups attached. US 7,789,958 B2 27 28

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation NValence Stabilizer #9: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional nitrogen Nitrogen Atoms and having at least one containing Substituents (usually amines) that additional Nitrogen Atom Binding Site not constitute N binding sites. Can include other in a Ring (NMonodentates, N N ring systems bound to the heterocyclic ring or to Bidentates, NTridentates, N. N. the N-containing Substituent, but they do not Tetradentates, or N N Hexadentates) 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 N containing Substituent(s) may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. NValence Stabilizer #10: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional nitrogen Nitrogen Atoms at least one additional containing Substituents (usually amines) that Nitrogen Atom Binding Site not in a Ring constitute N binding sites. Can include other (NMonodentates, N N Bidentates, N N ring systems bound to the heterocyclic ring or to Tridentates, N N Tetradentates, or N N the N-containing Substituent, but they do not Hexadentates) 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 N containing Substituent(s) may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. NValence Stabilizer #11: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional nitrogen Nitrogen Atoms at least one additional containing rings that constitute N binding sites. Nitrogen Atom Binding Site in a Separate Can include other ring systems bound to the N Ring (NMonodentates, N N Bidentates, N. N. containing heterocyclic rings, but they do not Tridentates, N N Tetradentates) 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 additional N-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. NValence Stabilizer #12: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional nitrogen Nitrogen Atoms at least one additional containing rings that constitute N binding sites. Nitrogen Atom Binding Site in a Separate Can include other ring systems bound to the N Ring (NMonodentates, N N Bidentates, N. N. containing heterocyclic rings, but they do not Tridentates, N N Tetradentates) 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 additional N-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. NValence Stabilizer #13: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, Six-, Eight-, and Ten six, eight, or ten nitrogen 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 Nitrogen (usually amine or metal ion. This ligand and or attached, imine groups) and are not contained in uncoordinating hydrocarbons rings may or may Component Heterocyclic Rings (N. N. not have halogen or polarizing or water Bidentates, N N Tridentates, N. N. insolubilizing solubilizing groups attached. Tetradentates, and N N Hexadentates) NValence Stabilizer #14: Macrocyclic ligands containing a total of four, Four-, Six-, Eight-, or Ten-Membered six, eight, or ten five-membered heterocyclic Macrocyclics, Macrobicyclics, and rings containing nitrogen 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 Nitrogen and are contained in Component metal ion. This ligand and or attached, 5-Membered Heterocyclic Rings (N-N uncoordinating hydrocarbon rings may or may Bidentates, N N Tridentates, N. N. not have halogen or polarizing or water US 7,789,958 B2 29 30

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Tetradentates, or N N Hexadentates) insolubilizing groups attached. NValence Stabilizer #15: Macrocyclic ligands containing at least one 5 Four-, Six-, Eight-, or Ten-Membered membered heterocyclic ring. These Macrocyclics, Macrobicyclics, and heterocyclic rings provide nitrogen binding sites Macropolycyclics (including Catapinands, to valence stabilize the central metalion. 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 four, six, Combination of 5-Membered Heterocyclic eight, or ten. Can include other Rings and Amine or Imine Groups (N-N hydrocarbon ring systems bound to this Bidentates, N N Tridentates, N. N. macrocyclic ligand, but they do not coordinate Tetradentates, or N N 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. NValence Stabilizer #16: Macrocyclic ligands containing a total of four, Four-, Six-, Eight-, or Ten-Membered six, eight, or ten six-membered heterocyclic Macrocyclics, Macrobicyclics, and rings containing nitrogen 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 Nitrogen and are contained in Component metal ion. This ligand and or attached, 6-Membered Heterocyclic Rings (N-N uncoordinating hydrocarbon rings may or may Bidentates, N N Tridentates, N. N. not have halogen or polarizing or water Tetradentates, or N N Hexadentates) insolubilizing groups attached. NValence Stabilizer #17: Macrocyclic ligands containing at east one 6 Four-, Six-, Eight-, or Ten-Membered membered heterocyclic ring. These Macrocyclics, Macrobicyclics, and heterocyclic rings provide nitrogen binding sites Macropolycyclics (including Catapinands, ovalence stabilize the central metalion. 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 he total number of binding sites is four, six, Combination of 6-Membered Heterocyclic eight, or ten. Can include other Rings and Amine or Imine Groups (N-N hydrocarbon ring systems bound to this Bidentates, N N Tridentates, N. N. macrocyclic ligand, but they do not coordinate Tetradentates, or N N Hexadentates) with the stabilized, high valence metal ion. This igand and/or attached, uncoordinating hydrocarbon rings may or may not have halogen or polarizing or water-insolubilizing groups attached. NValence Stabilizer #18: R" NH C(-R)=N R", where R, R', and R' Amidines and Diamidines (N. N. Bidentates represent H or any organic functional group and N N Tetradentates) wherein the number of carbon atoms ranges rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #19: RR N C(-NH) NR" C(-NH) NR"R" for Biguanides (Imidodicarbonimidic Diamides biguanides, RR' N–C(—NH)—NR" or Dihydrazides), Biguanidines, or biguanidines, where R, R', R", midotricarbonimidic Diamides or R", and R" represent H, NH, or any organic Dihydrazides, Imidotetracarbonimidic unctional group wherein the number of carbon Diamides or Dihydrazides, Dibiguanides, atoms ranges from 0 to 40, halogen or Bis(biguanidines), Polybiguanides, and polarizing or water-insolubilizing solubilizing Poly(biguanidines) (N. N. Bidentates, N N groups attached. Ligand can also contain Tridentates, N N Tetradentates, and N N nonbinding N, O, S, or Patoms. Hexadentates) NValence Stabilizer #20: RR N C(-NH) CR"R" C(-NH) NR"R" s Diamidinomethanes, where R, R', R", R", R", and R" represent Bis(amidinomethanes), and H, NH2, or any organic functional group Poly(amidinomethanes) (N-NBidentates, wherein the number of carbon atoms ranges N N Tridentates, N N Tetradentates, and N N rom 0 to 40, optionally having halogen or Hexadentates) polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #21: RR' N C(=NH)– NR" C(=NH) R" for midoylguanidines, Amidinoguanidines, imidoylguanidines, and RR'—N–C(—NH)—NR" Bis(imidoylguanidines), or amidinoguanidines, where Bis(amidinoguanidines), R. R', R", and R" represent H, NH, or any Poly(imidoylguanidines), and organic functional group wherein the number of Poly(amidinoguanidines) (N. N. Bidentates, carbon atoms ranges from 0 to 40, optionally N. N. Tridentates, N N Tetradentates) having halogen or polarizing or water insolubilizing solubilizing groups attached. US 7,789,958 B2 31 32

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #22: RR' N C(=NH)- O C(=NH)– NR"R", where R, Diformamidine oxides (Dicarbonimidic R", R", and R" represent H, NH, or any Diamides or Dihydrazides), organic functional group wherein the number of Tricarbonimidic Diamides or Dihydrazides, carbon atoms ranges from 0 to 40, optionally Tetracarbonimidic Diamides or having halogen or polarizing or water Dihydrazides, Bis(diformamidine oxides), insolubilizing solubilizing groups attached. and Poly(diformamidine oxides) (N-N Ligand can also contain nonbinding N, O, S, or Bidentates, N N Tridentates, N. N. Patoms. Tetradentates) NValence Stabilizer #23: RR' N C(=NH)–S C(=NH) NR"R", where R, Diformamidine Sulfides R", R", and R" represent H, NH, or any (Thiodicarbonimidic Diamides or organic functional group wherein the number of Dihydrazides), Thiotricarbonimidic carbon atoms ranges from 0 to 40, optionally Diamides or Dihydrazides, having halogen or polarizing or water Thiotetracarbonimidic Diamides or insolubilizing solubilizing groups attached. Dihydrazides, Bis(diformamidine sulfides), Ligand can also contain nonbinding N, O, S, or and Poly(diformamidine sulfides) (N-N Patoms. Bidentates, N N Tridentates, N. N. Tetradentates) NValence Stabilizer #24: R O C(=NH)– NR' C(=NH)–O R" for midodicarbonimidic Acids, imidodicarbomimidic acids, and R-O-C(—NH)—NR' NH-C(-NH)–O—R" Diimidodicarbonimidic Acids, O midotricarbonimidic Acids, diimidodicarbonimidic acids, where R, R', and midotetracarbonimidic Acids, and R" represent H, NH2, or any organic functional derivatives thereof (N. N. Bidentates, N N group wherein the number of carbon atoms Tridentates, N N Tetradentates, and N N ranges from 0 to 40, optionally having halogen Hexadentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #25: R-S C(=NH)– NR' C(=NH)–S R" for Thioimidodicarbonimidic Acids, hioimidodicarbonimidic acids, and R-S-C(—NH)—NR' NH-C(—NH)—S—R" Thiodiimidodicarbonimidic Acids, O Thioimidotricarbonimidic Acids, hiodiimidodicarbonimidic acids, where R, R', Thioimidotetracarbonimidic Acids, and and R' represent H, NH2, or any organic derivatives thereof (N. N. Bidentates, N N unctional group wherein the number of carbon Tridentates, N N Tetradentates, and N N atoms ranges from 0 to 40, optionally having Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #26: R C(=NH)– NR' C(=NH) R' for Diimidoylimines, Diimidoylhydrazides, diimidoylimines, and R-C(—NH)—NR' NH-C(-NH)—R" Bis(diimidoylimines), or diimidoylhydrazides, where R, Bis(diimidoylhydrazides), R', and R" represent H, NH2, or any organic Poly(diimidoylimines), and unctional group wherein the number of carbon Poly(diimidoylhydrazides) (N. N. atoms ranges from 0 to 40, optionally having Tridentates and N N Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #27: RR' N S(=NH)(=O) OR" or RR' N S(=NH)(=O) N. R"R" midosulfamides, Diimidosulfamides, or imidosulfamides, and Bis(imidosulfamides), RR' N S(=NH)(-NH) OR" or RR' N S(=NH)(-NH) N. R"R" Bis(diimidosulfamides), or diimidosulfamides, Poly(imidosulfamides), and where R, R, R", and R" represent H, NH, or Poly(diimidosulfamides) (N. N. Bidentates, any organic functional group wherein the N. N. Tridentates, N N Tetradentates, and N N number 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 Patoms. NValence Stabilizer #28: (NH-)P( NRR')( NR"R") ( NR"R"), where Phosphoramidimidic Triamides, R. R', R", R", R", and R" represent H, NH, Bis(phosphoramidimidic triamides), and or any organic functional group wherein the Poly(phosphoramidimidic triamides) and number of carbon atoms ranges from 0 to 40, derivatives thereof (N. N. Bidentates, N N optionally having halogen or polarizing or Tridentates, N N Tetradentates, and N N water-insolubilizing solubilizing groups Hexadentates) attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #29: (NH=)P(—NRR)(OH)2 for phosphoramidimidic Phosphoramidimidic Acid, acid, and (NH-)P( NRR") ( NR"R")(OH) for US 7,789,958 B2 33 34

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Phosphorodiamidimidic Acid, phosphorodiamidimidic acid, where R, R', R", Bis(Phosphoramidimidic Acid), and R" represent H, NH, or any organic Bis(Phosphorodiamidimidic Acid), unctional group wherein the number of carbon Poly(Phosphoramidimidic Acid), atoms ranges from 0 to 40, optionally having Poly(Phosphorodiamidimidic Acid), and halogen or polarizing or water derivatives thereof (N. N. Bidentates, N N insolubilizing solubilizing groups attached. Tridentates, N N Tetradentates, and N N Ligand can also contain nonbinding N, O, S, or Hexadentates) Patoms. NValence Stabilizer #30: Phosphoramidimidodithioic Acid, phosphoramidimidodithioic acid, and (NH-)P(—NRR") ( NR"R") (SH) Phosphorodiamidimidothioic Acid, O Bis(Phosphoramidimidodithioic Acid), phosphorodiamidimidothioic acid, where R, R, Bis(Phosphorodiamidimidothioic Acid), R", and R" represent H, NH, or any organic Poly(Phosphoramidimidodithioic Acid), unctional group wherein the number of carbon Poly(Phosphorodiamidimidothioic Acid), atoms ranges from 0 to 40, optionally having and derivatives thereof (N-NBidentates, N. N. halogen or polarizing or water Tridentates, N N Tetradentates, and N N insolubilizing solubilizing groups attached. Hexadentates) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #31: R-N=N-R' for azo compounds, R-N-N-NH-R' AZO compounds including triaZenes with or triaZenes, where R, and R' represent Hor amino, imino, oximo, diazeno, or hydrazido any organic functional group wherein the Substitution at the ortho-(for aryl) or alpha number of carbon atoms ranges from 0 to 40, or beta-(for alkyl) positions, Biso-(H2N–) optionally having halogen or polarizing or or alpha- or beta-(H2N-)azo compounds), or water-insolubilizing solubilizing groups Polyo-(H2N-) or alpha- or beta-(H2N-)azo attached. (Must include ortho-amino, imino, compounds) (N. N. Bidentates, N N oximo, diazeno, or hydrazido Substituted aryl Tridentates, N N Tetradentates, or N N aZo compounds, and alpha- or beta-amino, Hexadentates) imino, oximo, diaZeno, or hydrazido alkyl azo compounds.) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #32: R N=N C(=NH) NR'R' for Diazeneformimidamides diazeneformimidamides, and R-N=N–CRR"—C(=NH)—NR"R" (DiaZeneamidines), DiaZeneacetimidamides for diazeneacetimidamides, (Diazene-alpha-amidinoalkanes(alkenes)), where R, R', R", R", and R" represent H, Bis(diazeneformimidamides), NH2, or any organic functional group wherein Bis(diazeneacetimidamides), the number of carbon atoms ranges from 0 to Poly(diazeneformimidamides), and 40, optionally having halogen or polarizing or Poly(diazeneacetimidamides) (N. N. water-insolubilizing solubilizing groups Bidentates, N N Tetradentates, and N N attached. Ligand can also contain nonbinding N, Hexadentates) O, S, or Patoms. NValence Stabilizer #33: R-N=N-C(=NH)—OR' for diazeneformimidic DiaZeneformimidic Acid, acid, and R N=N CR'R' C(=NH) OR" for DiaZeneacetimidic Acid, diaZeneacetimidic acid, where R, R', R', and Bis(diazeneformimidic acid), R" represent H, NH2, or any organic functional Bis(diazeneacetimidic acid), group wherein the number of carbon atoms Poly(diazeneformimidic acid), ranges from 0 to 40, optionally having halogen Poly(diazeneacetimidic acid), and or polarizing or water derivatives thereof (N. N. Bidentates, N N insolubilizing solubilizing groups attached. Tetradentates, and N N Hexadentates) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #34: DiaZeneformimidothioic Acid, diazeneformimidothioic acid, and R-N=N–CRR"—C(=NH)—SR" DiaZeneacetimidothioic Acid, for Bis(diazeneformimidothioic acid), diazeneacetimidothioic acid, where R. R. R", Bis(diazeneacetimidothioic acid), and R" represent H, NH, or any organic Poly(diazeneformimidothioic acid), functional group wherein the number of carbon Poly(diazeneacetimidothioic acid), and atoms ranges from 0 to 40, optionally having derivatives thereof (N. N. Bidentates, N N halogen or polarizing or water Tetradentates, and N N Hexadentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #35: Imidoyldiazenes, Bis(imidoyldiazenes), and where R, R', R", and R" Poly(imidoyldiazenes), (N N Bidentates, N-N represent H, NH2, or any organic functional Tetradentates and N N Hexadentates) 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 Patoms. NValence Stabilizer #36: RR'—N–C(=NH)—N=N-C(-NH)—NR"R" for diazenediformimidamides, Diazenediformimidamides (1,2- and RR. N. C(-NH) CR"R" N=N CR"R" C(-NH) NR"R" DiaZenediamidines), for diazenediacetimidamides, where R. R. R", US 7,789,958 B2 35 36

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation DiaZenediacetimidamides (1,2-Diazene-di- R", R", R", R", and R" represent H, alpha-amidinoalkanes(alkenes)), NH2, or any organic functional group wherein Bis(diazenediformimidamides), the number of carbon atoms ranges from 0 to Bis(diazenediacetimidamides), 40, optionally having halogen or polarizing or Poly(diazenediformimidamides), and water-insolubilizing solubilizing groups Poly(diazenediacetimidamides) (N-N attached. Ligand can also contain nonbinding N, Tridentates and N N Hexadentates) O, S, or Patoms. NValence Stabilizer #37: RO C(=NH) N=N C(=NH) OR for DiaZenediformimidic Acid, diazenediformimidic acid, and RO C(=NH)–CR'R' N=N CR"R" C(=NH) OR" DiaZenediacetimidic Acid, O Bis(diazenediformimidic acid), diazenediacetimidic acid, where R, R', R", R", Bis(diazenediacetimidic acid), R", and R" represent H, NH, or any organic Poly(diazenediformimidic acid), and unctional group wherein the number of carbon Poly(diazenediacetimidic acid), and atoms ranges from 0 to 40, optionally having derivatives thereof (N N Tridentates and N. N. halogen or polarizing or water Hexadentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #38: RS C(=NH) N=N C(-NH) SR' for DiaZenediformimidothioic Acid, diazenediformimidothioic acid, and RS C(=NH)–CR'R' N=N CR"R" C(=NH)- SR" DiaZenediacetimidothioic Acid, or diaZenediacetimidothioic acid, where R, R, Bis(diazenediformimidothioic acid), R", R", R", and R" represent H, NH, or any Bis(diazenediacetimidothioic acid), organic functional group wherein the number of Poly(diazenediformimidothioic acid), and carbon atoms ranges from 0 to 40, optionally Poly(diazenediacetimidothioic acid), and having halogen or polarizing or water derivatives thereof (N N Tridentates and N. N. insolubilizing solubilizing groups attached. Hexadentates) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #39: R C(=NH)– N=N C(=NH) R' or Diimidoyldiazenes, Bis(diimidoyldiazenes), R C(-NH) CR'R''. N=N CR"R" C(-NH) R", and Poly(diimidoyldiazenes), (N N where R, Tridentates and N N Hexadentates) R", R", R", R", and R" represent H, NH, 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 Patoms. NValence Stabilizer #40: R N=N CR-N NR"R", where R, R', R", and Ortho-amino (or -hydrazido) Substituted R" represent H, or any organic functional Formazans, Bis(O-amino or -hydrazido group wherein the number of carbon atoms Substituted formazans), and Poly(o-amino ranges from 0 to 40, optionally having halogen or -hydrazido Substituted formazans) (N. N. or polarizing or water Bidentates, N N Tridentates, N. N. insolubilizing solubilizing groups attached. Tetradentates, and N N Hexadentates) (Must include ortho-amine or hydrazide substituted aryl R derivatives, and beta-amine or hydrazide substituted alkyl Riderivatives.) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #41: RRC=N N=CR"R" or RR'C=N NR"R" (for Ortho-amino (or -hydrazido) Substituted ketazines), where R, R', R", and R" represent Azines (including ketazines), Bis(O-amino H, or any organic functional group wherein the or hydrazido Substituted azines), and number of carbon atoms ranges from 0 to 40, Poly(o-amino or hydrazido Substituted optionally having halogen or polarizing or azines) (N-NBidentates, N N Tridentates, water-insolubilizing solubilizing groups N N Tetradentates, and N N Hexadentates) attached. (Must include ortho-amine or hydrazide substituted aryl Riderivatives, and beta-amine or hydrazide substituted alkyl R derivatives.) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #42: 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 with ortho- or alpha- or beta-amino or number of carbon atoms ranges from 0 to 40, imino or oximo or diazeno or hydrazido optionally having halogen or polarizing or Substitution (N. N. Bidentates, N N water-insolubilizing solubilizing groups Tridentates, N N Tetradentates, N. N. attached. (Must contain ortho- or alpha- or beta Pentadentates, or N N Hexadentates). Also amino or imino or oximo or diazeno or includes hydrazones with ortho-N hydrazido Substitution.) Ligand can also Substitution. contain nonbinding N, O, S, or Patoms. NValence Stabilizer #43: RRC. N. R.' N-CR'R' or R N C R. C. N. R. Schiff Bases with two Imine (C=N) Groups or RC–N R' N–CR", where R, R', R", R", and without ortho- (for aryl constituents) or and R" represent H, or any organic functional alpha- or beta- (for alkyl constituents) group wherein the number of carbon atoms hydroxy, carboxy, carbonyl, thiol, ranges from 0 to 40, optionally having halogen US 7,789,958 B2 37 38

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation mercapto, thiocarbonyl, amino, imino, or polarizing or water oximo, diazeno, or hydrazido Substitution insolubilizing solubilizing groups attached. (Not (N-NBidentates). Also includes including ortho-, alpha-, or beta-hydroxy, dihydrazones. carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido Substitution.) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #44: Schiff Bases with two Imine (C=N) Groups or RC–N R' N–CR", where R, R', R", R", and with ortho- or alpha- or beta-amino or and R" represent H, or any organic functional imino or oximo or diazeno or hydrazido group wherein the number of carbon atoms Substitution (N N Tridentates, N. N. ranges from 0 to 40, optionally having halogen Tetradentates, N N Pentadentates, or N N or polarizing or water Hexadentates). Also includes hydrazones insolubilizing solubilizing groups attached. with ortho-N substitution. (Must contain ortho- or alpha- or beta-amino or imino or oximo or diazeno or hydrazido Substitution.) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #45: N(—R-N=CR'R"), where R, R', and R" Schiff Bases with three Imine (C=N) represent H, or any organic functional group Groups and without ortho- (for aryl wherein the number of carbon atoms ranges constituents) or alpha- or beta- (for alkyl from 0 to 40, optionally having halogen or constituents) hydroxy, carboxy, carbonyl, polarizing or water-insolubilizing solubilizing thiol, mercapto, thiocarbonyl, amino, imino, groups attached. (Not including ortho-, alpha-, oximo, diazeno, or hydrazido Substitution or beta-hydroxy, carboxy, carbonyl, thiol, (N N Tridentates). Also includes mercapto, thiocarbonyl, amino, imino, oximo, trihydrazones. diazeno, or hydrazido Substitution.) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #46: N(—R-N=CR'R"), where R, R', and R' Schiff Bases with three Imine (C=N) represent H, or any organic functional group Groups and with ortho- or alpha- or beta wherein the number of carbon atoms ranges amino or imino or oximo or diazeno or rom 0 to 40, optionally having halogen or hydrazido Substitution (N-N Tetradentates, polarizing or water-insolubilizing solubilizing N N Pentadentates, or N N Hexadentates) groups attached. (Must contain ortho- or alpha or beta-amino or imino or oximo or diazeno or hydrazido Substitution.) Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #1: Macrocyclic ligands containing two, four, or six Macrocyclic, Macrobicyclic, and hioketone binding sites to valence stabilize the Macropolycyclic Oligothioketones central metalion. Can include other (including Catapinands, Cryptands, hydrocarbon or ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Thioketones with the stabilized, high valence metal ion. This (typically in the beta position) (S–S igand and/or attached, uncoordinating Bidentates, S-S Tetradentates, and S-S hydrocarbons rings may or may not have Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. SValence Stabilizer #2: Macrocyclic ligands containing two, four, six, Macrocyclic, Macrobicyclic, and or eight 1,1-dithiolene binding sites to valence Macropolycyclic Dithiolenes (including stabilize the central metalion. Can include other Catapinands, Cryptands, Cyclidenes, and hydrocarbon or ring systems bound to this Sepulchrates) wherein all Binding Sites are macrocyclic ligand, but they do not coordinate composed of alpha, alpha dithiols (meaning with the stabilized, high valence metal ion. This two thiol groups on a single carbon atom in igand and/or attached, uncoordinating he ring) (S–S Bidentates, S-S hydrocarbons rings may or may not have Tetradentates, and S-S Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. SValence Stabilizer #3: RC(=S) NR' C(=S) R' for Dithioimidodialdehydes, dithioimidodialdehydes, and RC(=S)—NR' NH-C(=S)—R" Dithiohydrazidodialdehydes (thioacyl or dithiohydrazidodialdehydes hiohydrazides), (thioacyl thiohydrazides), where R, R', and R" Bis(dithioimidodialdehydes), represent H, NH2, or any organic functional Bis(dithiohydrazidodialdehydes), group wherein the number of carbon atoms Poly(dithioimidodialdehydes), and ranges from 0 to 40, optionally having halogen Poly(dithiohydrazidodialdehydes) (S–S or polarizing or water Bidentates, S-S Tridentates, S-S insolubilizing solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #4: Dithioimidodicarbonic acids, for dithioimidodicarbonic Dithiohydrazidodicarbonic acids, Bis(dithioimidodicarbonic acids), R-S C(=S) NR' NH C(=S) S. R" for Bis(dithiohydrazidodicarbonic acids), dithiohydrazidodicarbonic acids, where R, R', Poly(dithioimidodicarbonic acids), and R' represent H, NH2, or any organic US 7,789,958 B2 39 40

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Poly(dithiohydrazidodicarbonic acids) and unctional group wherein the number of carbon derivatives thereof (S–S Bidentates, S-S atoms ranges from 0 to 40, optionally having Tridentates, S-S Tetradentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #5: R C(=S)-CR'R' C(=S)-R" where R, R', R", ,3-Dithioketones (Dithio-beta-ketonates), and R" represent H, NH2, or any organic ,3,5-Trithioketones, Bis(1,3- unctional group wherein the number of carbon Dithioketones), and Poly(1,3- atoms ranges from 0 to 40, optionally having Dithioketones) (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 Patoms. SValence Stabilizer #6: R-C(=S)—C(=S)—R' where Rand R' represent H, 2-Dithioketones (Dithiolenes, Dithio NH2, or any organic functional group wherein alpha-ketonates), 1,2,3-Trithioketones, he number of carbon atoms ranges from 0 to Dithiotropolonates, ortho-Dithioquinones, 40, optionally having halogen or polarizing or Bis(1,2-Dithioketones), and Poly(1,2- water-insolubilizing solubilizing groups Dithioketones) (S–S Bidentates, S-S attached. Ligand can also contain nonbinding N, Tridentates, S-S Tetradentates) O, S, or Patoms. SValence Stabilizer #7: RR' N C(=S) CR"R" C(=S)- N R"R" where Dithiomalonamides R. R', R", R", R", and R" represent H, NH, (Dithiomalonodiamides), or any organic functional group wherein the Bis(dithiomalonamides), and number of carbon atoms ranges from 0 to 40, Polydithiomalonamides (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 Patoms. SValence Stabilizer #8: RR' N C(=S) CR"R" C(=S)-R" where R, R', 2-Thioacylthioacetamides, Bis(2- R", R", and R" represent H, NH, or any thioacylthioacetamides), and Poly(2- organic functional group wherein the number of thioacylthioacetamides) (S–S Bidentates, S.–S carbon atoms ranges from 0 to 40, optionally Tridentates, S-S Tetradentates) having halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #9: R—C(=S)—S—C(=S)—R' where Rand R' represent Dithioacyl sulfides, Bis(dithioacyl sulfides), H or any organic functional group wherein the and Poly(dithioacyl sulfides) (S–S number of carbon atoms ranges from 0 to 40, Bidentates, S-S Tridentates, S-S optionally having halogen or polarizing or Tetradentates) water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #10: RR' N C(=S)–S C(=S)- N R"R" where R, R', Trithiodicarbonic Diamides, R", and R" represent H, NH2 or any organic Bis(trithiodicarbonic diamides), and unctional group wherein the number of carbon Poly(trithiodicarbonic diamides) (S–S atoms ranges from 0 to 40, optionally having Bidentates, S-S Tridentates, S-S halogen or polarizing or water Tetradentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #11: R-S-C(—S)—S-C(=S)—S-R' for Pentathio-, Tetrathio-, or Trithiodicarbonic pentathiodicarbonic acids, R-O-C(=S)—S-C(=S)—S-R' Acids, Bis(pentathio-, tetrathio-, or or tetrathiodicarbonic acids, and R-O-C(=S)—S-C(—S)—O—R' trithiodicarbonic acids), Poly(pentathio-, or pentathiodicarbonic tetrathio-, or trithiodicarbonic acids), and acids, where RandR' represent H, NH2 or any derivatives thereof (S–S Bidentates, S-S organic functional group wherein the number of Tridentates, S-S 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 SValence Stabilizer #12: Dithiohypophosphoric Acids, Bis(dithiohypophosphoric acids), and Poly(dithiohypophosphoric acids), and derivatives thereof (S–S Bidentates, S-S R, R', R", and R" represent H, NH2 or any Tridentates, S-S 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 Patoms. Note: these ligands are not to be US 7,789,958 B2 41 42

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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. SValence Stabilizer #13: (RR' N )(R"R" N )P(=S) P(=S)( N R"R") ( N R"R"), Dithiohypophosphoramides, where R, R', R", R", Bis(dithiohypophosphoramides), and R", R", R", and R" represent H, NH, or Poly(dithiohypophosphoramides) (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 Patoms. 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. SValence Stabilizer #14: (R-O-)(R'—O-)P(=S)—NH-P(=S)(-O-R")(-O-R"); Dithioimidodiphosphoric Acids, (R-O-)(R'—S—)P(=S)(—S—R")–(-NH-P(=S) (—S—R") ( O—R"); Dithiohydrazidodiphosphoric Acids, or (R-S )(R'—S—)P(—S)—NH-P(—S)(—S—R")(—S—R") Bis(dithioimidodiphosphoric Acids), or dithioimidodiphosphoric acids, and —NH-NH Bis(dithiohydrazidodiphosphoric Acids), derivatives for Poly(dithioimidodiphosphoric Acids), dithiohydrazidodiphosphoric acids, where R, Poly(dithiohydrazidodiphosphoric Acids), R", R", and R" represent H, NH2 or any organic and derivatives thereof (S–S Bidentates, S.–S unctional group wherein the number of carbon Tridentates, S-S 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 SValence Stabilizer #15: Dithioimidodiphosphoramides, Dithiohydrazidodiphosphoramides, ithioimidophosphoramides, and Bis(dithioimidodiphosphoramides), Bis(dithiohydrazidodiphosphoramides), ithiohydrazidodiphosphoramides, where R, R', Poly(dithioimidodiphosphoramides), and R", R", R", R", R", and R" represent Poly(dithiohydrazidodiphosphoramides) (S–S H, NH2 or any organic functional group wherein Bidentates, S-S Tridentates, S-S he 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, SValence Stabilizer #16: Dithiodiphosphoramides, Bis(dithioiphosphoramides), and where R, R', R", R", R", R", Poly(dithiodiphosphoramides) (S–S R", and R" represent H, NH, or any Bidentates, S-S Tridentates, S-S organic functional group wherein the number of 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 SValence Stabilizer #17: Dithiodiphosphoric Acids, Bis(dithioiphosphoric Acids), Poly(dithiodiphosphoric Acids), and Tridentates, S-S Tetradentates) where R, R', R", 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. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #18: (O—)P(—S—R)(—S-R')(—S—R") or (S—)P(—S—R)(—S-R')(-O-R"), Trithiophosphoric Acids where R, R', and R" represent H, (Phosphorotrithioic Acids), NH2 or any organic functional group wherein Bis(trithiophosphoric acids), the number of carbon atoms ranges from 0 to Poly(trithiophosphoric acids), and 40, optionally having halogen or polarizing or derivatives thereof (S–S Bidentates, S-S water-insolubilizing solubilizing groups US 7,789,958 B2 43 44

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Tridentates, S-S Tetradentates) attached. Ligand can also contain nonbinding N, SValence Stabilizer #19: Dithiophosphoric Acids (Phosphorodithioic where R, R', and R" represent H, Acids), Bis(dithiophosphoric acids), NH2 or any organic functional group wherein Poly(dithiophosphoric acids), and the number of carbon atoms ranges from 0 to derivatives thereof (S–S Bidentates, S-S 40, optionally having halogen or polarizing or Tridentates, S-S Tetradentates) water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #20: (S—)P(—S—R)(—S-R') (—S—R"), where R, R', and R" Tetrathiophosphoric Acids represent H, NH2 or any organic functional (Phosphorotetrathioic Acids), group wherein the number o carbon atoms Bis(tetrathiophosphoric acids), ranges from 0 to 40, optiona ly having halogen Poly(tetrathiophosphoric 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 SValence Stabilizer #21: Phosphoro(dithioperoxo)dithioic Acids, where R, R', and R' Bisphosphoro(dithioperoxo)dithioic represent H, NH2 or any organic functional Acids, group wherein the number o carbon atoms Polyphosphoro (dithioperoxo)dithioic ranges from 0 to 40, optiona ly having halogen Acids, and derivatives thereof (S–S or polarizing or water Bidentates, S-S Tridentates, S-S insolubilizing solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #22: Phosphoro(dithioperoxo)thioic Acids, Bisphosphoro(dithioperoxo)thioic Acids, represent H, NH2 or any organic functional Polyphosphoro (dithioperoxo)thioic Acids, group wherein the number o carbon atoms and derivatives thereof (S–S Bidentates, S.–S ranges from 0 to 40, optiona ly having halogen Tridentates, S-S Tetradentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #23: (S—)P(—S-S-R)(—S—R)(—S—R"), where R, R', and Phosphoro(dithioperoxo)trithioic Acids, R" represent H, NH2 or any organic functional Bisphosphoro(dithioperoxo)trithioic group wherein the number of carbon atoms Acids, ranges from 0 to 40, optionally having halogen Polyphosphoro (dithioperoxo)trithioic 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 ) Patoms. SValence Stabilizer #24: R-CR" (—SH)—CH2—C(=S)—R", where R, R', and Beta-Mercaptothioketones, Beta R" represent H, NH2 or any organic functional Mercaptothioaldehydes, Bis(beta group wherein the number of carbon atoms mercaptothioketones), Bis(beta ranges from 0 to 40, optionally having halogen mercaptothioaldehydes), Poly(beta or polarizing or water mercaptothioketones), and Poly(beta insolubilizing solubilizing groups attached. mercaptothioaldehydes) (S–S Bidentates, S-S Ligand can also contain nonbinding N, O, S, or Tridentates, S-S Tetradentates) Patoms. SValence Stabilizer #25: RR' N CH(-SH) NR" C(=S) NR"R", where N-(Aminomethylthiol)thioureas N R. R', R", R", and R" represent H, NH2 or any (Aminomercaptomethyl)thioureas), BisN organic functional group wherein the number of (aminomethylthiol)thioureas), and Poly N carbon atoms ranges from O to 40, optionally (aminomethylthiol)thioureas (S–S having halogen or polarizing or water Bidentates, S-S Tridentates, S-S insolubilizing solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #26: RR' N C(=S)- C(=S)- N R"R", where R, R', Dithiooxamides, Bis(dithiooxamides), and R", and R" represent H, NH, or any organic Poly(dithiooxamides) (S–S Bidentates, S.–S unctional group wherein the number of carbon Tridentates, S-S 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 Patoms. SValence Stabilizer #27: RR'—C—C(—S)(—S), where Rand R' represent H, 1,1-Dithiolates, Bis(1,1-dithiolates), and NH2 or any organic functional group wherein Poly(1,1-dithiolates) (S–S Bidentates and S-S he number of carbon atoms ranges from 0 to Tetradentates) 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups US 7,789,958 B2 45 46

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #28: R—C(=S)(—S-R') for dithiomonocarboxylic acids, Dithiomonocarboxylic Acids, Tri- and and (R-S )(S—)C—R'—C(=S)(—S—R") for tri- and Tetrathiodicarboxylic Acids, tetrathiodicarboxylic acids, where R, R', and R" Bis(dithiomonocarboxylic Acids), Bis(tri represent H, NH2 or any organic functional and tetrathiodicarboxylic acids), group wherein the number of carbon atoms Poly(dithiomonocarboxylic acids), Poly(tri ranges from 0 to 40, optionally having halogen and tetrathiodicarboxylic acids), and or polarizing or water derivatives thereof (S–S Bidentates and S-S insolubilizing solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #29: R-C(=S)(-S-S-R') for perthiomonocarboxylic Perthiomonocarboxylic Acids, acids, and (R-S-S-)(S—)C—R' C(=S)(-S-S-R") Perthiodicarboxylic Acids, or perthiodicarboxylic acids, where R, R', and Bis(perthiomonocarboxylic acids), R" represent H, NH2 or any organic functional Bis(perthiodicarboxylic acids), group wherein the number of carbon atoms Poly(perthiomonocarboxylic acids), ranges from 0 to 40, optionally having halogen Poly(perthiodicarboxylic acids), and or polarizing or water derivatives thereof (S–S Bidentates and S-S insolubilizing solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #30: R-S-C(—S)—O—R' or R-S-C(=O)—S-R' for Dithiocarbonates, Trithiocarbonates, dithiocarbonates, R-S-C(=S)—S-R' for Perthiocarbonates, Bis(dithiocarbonates), trithiocarbonates, and R-S-S-C(—S)—S-R' for Bis(trithiocarbonates), and perthiocarbonates, where R, and R' represent H, Bis(perthiocarbonates) (S–S Bidentates and NH2 or any organic functional group wherein S–S Tetradentates) he 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 Patoms. SValence Stabilizer #31: RR'N'=C(SH)(SH), where Rand R' represent Dithiocarbamates, Bis(dithiocarbamates), H, OH, SH, OR" (R" = C-Co alkyl or aryl), and Poly(dithiocarbamates) (including N SR" (R" = C-Co alkyl or aryl), NH2 or any hydroxydithiocarbamates and N organic functional group wherein the number of mercaptodithiocarbamates) (S–S Bidentates, carbon atoms ranges from 0 to 40, optionally S–S Tridentates, and S-S Tetradentates) having halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #32: RRN NR" C(=S)(SH), where R and R' Dithiocarbazates (Dithiocarbazides), represent H, NH2 or any organic functional Bis(dithiocarbazates), and group wherein the number of carbon atoms Poly(dithiocarbazates) (S–S Bidentates, S-S ranges from 0 to 40, optionally having halogen Tridentates, and S-S 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 Patoms. SValence Stabilizer #33: Thiocyanates bound directly to the high valence Thiocyanate ligands (S Monodentates) metal ion. OValence Stabilizer #1: RR N C(=O) NR" C(=O) NR"R" for Biurets (Imidodicarbonic Diamides), biurets, and RR' N C(=O) NR" NH C(=O) NR"R" Isobiurets, Biureas, Triurets, Triureas, orbiureas, where R, R', R", R", and Bis(biurets), Bis(isobiurets), Bis(biureas), R" represent H, NH2, or any organic functional Poly(biurets), Poly(isobiurets), and group wherein the number of carbon atoms Poly(biureas) (O-O Bidentates, O—O ranges from 0 to 40, optionally having halogen Tridentates, O-O Tetradentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #2: RR' N C(=O) NR" C(=O)-R" where R, R', Acylureas, Aroylureas, Bis(acylureas), R", and R" represent H, NH, or any organic Bis(aroylu reas), Poly(acylureas), and unctional group wherein the number of carbon Poly(aroylureas) (O-O Bidentates, O—O atoms ranges from 0 to 40, optionally having Tridentates, O-O Tetradentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #3: RC(=O)—NR'—C(=O)—R" for imidodialdehydes, Imidodialdehydes, Hydrazidodialdehydes and RC(=O) NR' NH C(=O) R' for (Acyl hydrazides), Bis(imidodialdehydes), hydrazidodialdehydes (acyl hydrazides), where Bis(hydrazidodialdehydes), R, R', and R' represent H, NH2, or any organic Poly(imidodialdehydes), and unctional group wherein the number of carbon US 7,789,958 B2 47 48

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Poly(hydrazidodialdehydes) (O-O atoms ranges from 0 to 40, optionally having Bidentates, O-O Tridentates, O O halogen or polarizing or water Tetradentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #4: R-O-C(=O)—NR'—C(=O)—O-R" for Imidodicarbonic acids, imidodicarbonic acids, and R-O-C(=O)—NR' Hydrazidodicarbonic acids, or hydrazidodicarbonic acids, Bis(imidodicarbonic acids), where R, R', and R" represent H, NH2, or any Bis(hydrazidodicarbonic acids), organic functional group wherein the number of Poly(imidodicarbonic acids), carbon atoms ranges from 0 to 40, optionally Poly(hydrazidodicarbonic acids) and having halogen or polarizing or water derivatives thereof (O-O Bidentates, O—O insolubilizing solubilizing groups attached. Tridentates, O-O Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #5: Imidodisulfamic Acid, Imidodisulfuric or imidodisulfamic acid, and R-O-S(=O)(=O)—NR' Acid, Bis(Imidodisulfamic Acid), or imidosulfuric acid, Bis(Imidodisulfuric Acid), where R, R', and R" represent H, NH2, or any Poly(Imidodisulfamic Acid), and organic functional group wherein the number of Poly(Imidodisulfuric Acid) and derivatives carbon atoms ranges from 0 to 40, optionally thereof (O-O Bidentates, O-O Tridentates, having halogen or polarizing or water O-O Tetradentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #6: 1,3-Diketones (Beta-Diketonates), 1,3,5- and R" represent H, NH2, or any organic Triketones, Bis(1,3-Diketones), and unctional group wherein the number of carbon Poly(1,3-Diketones), all with a Molecular atoms ranges from 0 to 40, optionally having Weight Greater than 125 (O-O Bidentates, halogen or polarizing or water O—O Tridentates, O-O Tetradentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. If these ligands exhibit a molecular weight less than or equal to 125, the solubility of the resultant Mn-diketonate complex will be too high. OValence Stabilizer #7: 1,2-Diketones (Alpha-Diketonates), 1,2,3- H, NH2, or any organic functional group Triketones, Tropolonates, ortho-Quinones, wherein the number of carbon atoms ranges Bis(1,2-Diketones), and Poly(1,2- rom 0 to 40, optionally having halogen or Diketones), all with a Molecular Weight polarizing or water-insolubilizing solubilizing Greater than 100 (O-O Bidentates, O—O groups attached. Ligand can also contain Tridentates, O-O Tetradentates) nonbinding N, O, S, or Patoms. If these ligands exhibit a molecular weight less than or equal to 100, the solubility of the resultant Mn'- diketonate complex will be too high. OValence Stabilizer #8: Malonamides (Malonodiamides), where R, R', R", R", R", and R" represent H, Bis(malonamides), and Polymalonamides NH2, or any organic functional group wherein (O-O Bidentates, O-O Tridentates, O—O 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 Patoms. OValence Stabilizer #9: 2-Acylacetamides, Bis(2-acylacetamides), R", R", and R" represent H, NH, or any and Poly(2-acylacetamides) (O-O organic functional group wherein the number of Bidentates, O-O Tridentates, O O 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 Patoms. OValence Stabilizer #10: Monothiodicarbonic Diamides, R", and R" represent H, NH2 or any organic Bis(monothiodicarbonic diamides), and unctional group wherein the number of carbon Poly(monothiodicarbonic diamides) (O-O atoms ranges from 0 to 40, optionally having Bidentates, O-O Tridentates, O O halogen or polarizing or water Tetradentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #11: Monothiodicarbonic Acids, represent H, NH2 or any organic functional Bis(monothiodicarbonic acids), group wherein the number of carbon atoms Poly(monothiodicarbonic acids), and ranges from 0 to 40, optionally having halogen US 7,789,958 B2 49 50

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 Patoms. OValence Stabilizer #12: R-O-S(=O)(—O)—S-S(-O)(=O)—O—R', where R Trithionic acid, Bis(trithionic acid), and R' represent H, NH2 or any organic Poly(trithionic acid), and derivatives functional group wherein the number of carbon thereof (O-O Bidentates, O-O Tridentates, atoms ranges from 0 to 40, optionally having O-O Tetradentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #13: (R-O-)(R'—O-)P(=O)—P(=O)(-O-R") (—O—R"), Hypophosphoric Acids, where R, R', R", and R" represent H, NH2 or Bis(hypophosphoric acids), and any organic functional group wherein the Poly(hypophosphoric acids), and number of carbon atoms ranges from 0 to 40, derivatives thereof (O-O Bidentates, O—O optionally having halogen or polarizing or Tridentates, O-O Tetradentates) water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. 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. OValence Stabilizer #14: Hypophosphoramides, where R, R', R", R", Bis(hypophosphoramides), and R", R", R", and R" represent H, NH, or Poly(hypophosphoramides) (O-O any organic functional group wherein the Bidentates, O-O Tridentates, O 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 Patoms. Note: these ligands are not to be confused with hypophosphorous acid erivatives (hypophosphites) (R-O-)R"R"P(=O) which are very reducing and herefore unacceptable for stabilization of high valence states in metal ions. OValence Stabilizer #15: (R-O )(R'-O-)P(=O) NH P(=O)( O R") ( O R") Imidodiphosphoric Acids, or imidodiphosphoric acids, and Hydrazidodiphosphoric Acids, (R-O )(R'-O-)P(=O) NH-NH P(=O)( O R")(-O-R") Bis(imidodiphosphoric Acids), or hydrazidodiphosphoric acids; where R, R', Bis(hydrazidodiphosphoric Acids), R", and R" represent H, NH, or any organic Poly(imidodiphosphoric Acids), unctional group wherein the number of carbon Poly(hydrazidodiphosphoric 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 Patoms. OValence Stabilizer #16: (RR' N )(R"R" N )P(=O) NH P(=O)( N R"R") ( N R"R") Imidodiphosphoramides, O Hydrazidodiphosphoramides, imidodiphosphoramides, and —NH-NH Bis(imidodiphosphoramides), derivatives for hydrazidodiphosphoramides, Bis(hydrazidodiphosphoramides), where R, R', R", R", R", R", R", and Poly(imidodiphosphoramides), and R" represent H, NH, or any organic Poly(hydrazidodiphosphoramides) (O-O unctional group wherein the number of carbon Bidentates, O-O Tridentates, O O atoms ranges from 0 to 40, optionally having Tetradentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #17: (RR' N )(R"R" N )P(=O)- O P(=O)( N R"R") ( N R"R"), Diphosphoramides, Bis(diphosphoramides), where R, R', R", R", and Poly(diphosphoramides) (O-O R", R", R", and R" represent H, NH, or Bidentates, O-O Tridentates, O O any organic functional group wherein the Tetradentates) 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 Patoms. OValence Stabilizer #18: R-CR'(-OH)—CH2—C(=O)—R", where R, R', and Beta-Hydroxyketones, Beta R" represent H, NH2 or any organic functional Hydroxyaldehydes, Bis(beta group wherein the number of carbon atoms US 7,789,958 B2 51 52

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation hydroxyketones), Bis(beta ranges from 0 to 40, optionally having halogen hydroxyaldehydes), Poly(beta or polarizing or water hydroxyketones), and Poly(beta insolubilizing solubilizing groups attached. hydroxyaldehydes) (O-O Bidentates, O—O Ligand can also contain nonbinding N, O, S, or Tridentates, O-O Tetradentates) Patoms. OValence Stabilizer #19: RR' N CH(-OH)– NR" C(=O) NR"R", where N-(Aminomethylol)ureas N R. R', R", R", and R" represent H, NH2 or any (Aminohydroxymethyl)ureas, BisN organic functional group wherein the number of (aminomethylol)ureas, and Poly N carbon atoms ranges from 0 to 40, optionally (aminomethylol)ureas (O-O Bidentates, O—O having halogen or polarizing or water Tridentates, O-O Tetradentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #20: RR' N C(=O) C(=O)- N R"R", where R, R', Oxamides, Bis(oxamides), and R", and R" represent H, NH2 or any organic Poly(oxamides) (O-O Bidentates, O—O unctional group wherein the number of carbon Tridentates, O-O 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 Patoms. OValence Stabilizer #21: —C(-OH)—C(-OH)—, where the two carbon atoms Squaric Acids and derivatives thereof (O-O Supporting the hydroxy groups are included Bidentates) within a cyclic hy rocarbon moiety, optionally having halogen or polarizing or water insolubilizing solu bilizing groups attached. Ligand can also cointain nonbinding N, O, S, or Patoms. OValence Stabilizer #22: Dicarboxylic Acids, Bis(dicarboxylic and R" represent H , NH2 or any organic acids), Poly(dicarboxylic acids), and unctional group wherein the number of carbon derivatives thereof (O-O Bidentates and O—O atoms ranges from O to 40, optionally having Tetradentates) halogen or polarizing or water insolubilizing solu bilizing groups attached. Ligand can also cointain nonbinding N, O, S, or Patoms. OValence Stabilizer #23: RR'N'=C(OH)(OH), where R and R' represent Carbamates, Bis(carbamates), and H, OH, SH, OR" (R" = C-Co alkyl or aryl), Poly(carbamates) (including N SR" (R" = C-Co alkyl or aryl), NH2 or any hydroxycarbamates and N organic functional group wherein the number of mercaptocarbamates) (O-O Bidentates, O—O carbon atoms ranges from 0 to 40, optionally Tridentates, and O-O Tetradentates) having halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #24: RN=C(OH)(OH), where R represents H, NH, or Carbimates, Bis(carbimates), and any organic functional group wherein the Poly(carbimates) (O-O Bidentates, O-O number of carbon atoms ranges from 0 to 40, Tridentates, and O-O Tetradentates) optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #25: Cyanates bound directly to the high valence Cyanate ligands (O Monodentates) metal ion. N-S Valence Stabilizer #1: RR' N C(=NH)–S–S C(-NH) NR"R", where Diformamidine Disulfides R, R', R", and R" represent H, NH, or any (Thioperoxydicarbonimidic Diamides or organic functional group wherein the number of Dihydrazides), Thioperoxytricarbonimidic carbon atoms ranges from 0 to 40, optionally Diamides or Dihydrazides, having halogen or polarizing or water Thioperoxytetracarbonimidic Diamides or insolubilizing solubilizing groups attached. Dihydrazides, Bis(diformamidine Ligand can also contain nonbinding N, O, S, or disulfides), and Poly(diformamidine Patoms. disulfides) (N–S Bidentates, N–S Tridentates, N–S Tetradentates) N-S Valence Stabilizer #2: RR' N C(=NH)–S. CS NR"R", where R, R', S-Amidinodithiocarbamates, Bis(S- R", and R" represent H, NH2 or any organic amidinodithiocarbamates), and Poly(S- unctional group wherein the number of carbon amidinodithiocarbamates) (N–S Bidentates atoms ranges from 0 to 40, optionally having and N–S Tetradentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #3: RR' N C(=NH)- O CS NR"R", where R, R', O-Amidinothiocarbamates, Bis(O- R", and R" represent H, NH2 or any organic US 7,789,958 B2 53 54

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation amidinothiocarbamates), and Poly(O- unctional group wherein the number of carbon amidinothiocarbamates) (N-S Bidentates atoms ranges from 0 to 40, optionally having and N–S Tetradentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #4: RR' N C(=NH)–S–S CS NR"R", where R, R', S-Amidinoperoxythiocarbamates, Bis(S- R", and R" represent H, NH2 or any organic amidinoperoxythiocarbamates), and Poly(S- unctional group wherein the number of carbon amidinoperoxythiocarbamates) (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 Patoms. N-S Valence Stabilizer #5: (NH=)P(-SR)(-OR)(-OR") for Phosphorimidothioic Acid; phosphorimidothioic acid, (NH-)P(—SR)(—SR)(-OR") Phosphorimidodithioic Acid: or phosphorimidodithioic acid, (NH-)P(—SR)(—SR)(—SR") Phosphorimidotrithioic Acid; or phosphorimidotrithioic Bis(Phosphorimidothioic Acid); acid, where R, R', and R" represent H, NH2 or Bis(Phosphorimidodithioic Acid); any organic functional group wherein the Bis(Phosphorimidotrithioic Acid); number of carbon atoms ranges from 0 to 40, Poly(Phosphorimidothioic Acid); optionally having halogen or polarizing or Poly(Phosphorimidodithioic Acid); water-insolubilizing solubilizing groups Poly(Phosphorimidotrithioic Acid); and attached. Ligand can also contain nonbinding N, derivatives thereof (N–S Bidentates and N–S O, S, or Patoms. Tetradentates) N-S Valence Stabilizer #6: (S-)P( NRR')( NR"R") ( NR"R"), where R, Phosphorothioic Triamides, R", R", R", R", and R" represent H, NH, or Bis(phosphorothioic triamides), and any organic functional group wherein the Poly(phosphorothioic triamides) (N–S number of carbon atoms ranges from 0 to 40, Bidentates and N–S Tetradentates) optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #7: (S-)P( NRR')(-SR")(- SR") for Phosphoramidotrithioic Acid, phosphoramidotrithioic acid, and (S-)P(—NRR") ( NR"R") (—SR") Phosphorodiamidodithioic Acid, O Bis(phosphoramidotrithioic acid), phosphorodiamidodithioic acid, where R, R, Bis(phosphorodiamidodithioic acid), R", R", and R" represent H, NH2 or any poly(phosphoramidotrithioic acid), organic functional group wherein the number of poly(phosphorodiamidodithioic acid), 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 Patoms. N-S Valence Stabilizer #8: (O-)P( NRR") ( SR") ( OR") or (S-)P( NRR')(-OR") ( OR") Phosphoramidothioic Acid, orphosphoramidothioic Phosphoramidodithioic Acid, Phosphorodiamidothioic Acid, O Bis(Phosphoramidothioic Acid), phosphoramidodithioic acid; (O—)P(—NRR") (—NR"R") (—SR") Bis(Phosphoramidodithioic Acid), or (S-)P( NRR)( NR"R") ( OR") Bis(Phosphorodiamidothioic Acid), orphosphorodiamidothioic acid, where Poly(Phosphoramidothioic Acid), R. R', R", R", and R" represent H, NH2 or any Poly(Phosphoramidodithioic Acid), and organic functional group wherein the number of Poly(Phosphorodiamidothioic Acid) (N–S carbon atoms ranges from 0 to 40, optionally Bidentates and N-S Tetradentates) having halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #9: R' C(=S)-N=C(—R)(-NHR"), where R is an N. Thioacyl 7-Aminobenzylidenimines (N–S aromatic derivative (i.e. —CHs), and Rand R' Bidentates or N-S Tetradentates) 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. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #10: R C(=S) NR’ OH or R C(-SH)=N OH, where Thiohydroxamates (Thiohydroxylamines), Rand R' represent H, NH2 or any organic Bis(thiohydroxamates), and functional group wherein the number of carbon Poly(thiohydroxamates) (N-S Bidentates, atoms ranges from 0 to 40, optionally having N–S Tetradentates, and N–S Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. US 7,789,958 B2 55 56

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #11: R-CH( NHR') C(=S)(-OH) or R CH( NHR') C(=S)(-SH) Alpha- or ortho-Aminothiocarboxylic or aminothiocarboxylic acids, and Acids, and alpha- or ortho- (HO )(S=)C CH( NHR) R' CH( NHR") C(=S)(-OH) Aminothiodicarboxylic Acids, and or (HS )(S=)C CH( NHR) R' CH( NHR") C(=S)(-SH) derivatives thereof (N–S Bidentates, N–S O Tridentates, and N–S Tetradentates) aminothiodicarboxylic acids, where R, R', and R" represent any organic functional group wherein the number of carbon atoms ranges rom 1 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #12: RR' N C(=S)- NR" N=CR"R", where R, R', Thiosemicarbazones, R", R", and R" represent H, or any organic Bis(thiosemicarbazones), and unctional group wherein the number of carbon Poly(thiosemicarbazones) (N–S Bidentates, atoms ranges from 0 to 40, optionally having N–S Tetradentates, and N–S Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #13: R C(=S)- NR N=CR"R", where R, R', R", and Thioacyl hydrazones, Bis(thioacyl R" represent H, or any organic functional hydrazones), and Poly(thioacyl hydrazones) group wherein the number of carbon atoms (N–S Bidentates, N–S Tetradentates, and N–S ranges from 0 to 40, optionally having halogen Hexadentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #14: R N=N C(=S) NR' NR"R", where R, R', R", Thiocarbazones (DiaZenecarbothioic and R" represent H, or any organic functional hydrazides), Bis(thiocarbazones), and group wherein the number of carbon atoms Poly(thiocarbazones) (N–S Bidentates, N–S ranges from 0 to 40, optionally having halogen Tetradentates, and N–S Hexadentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #15: R-N=N-R' for azo compounds, R N=N. NH-R' AZO compounds including triaZenes with for triaZenes, where R, and R' represent Hor hiol or mercapto or thiocarbonyl any organic functional group wherein the Substitution at the ortho- (for aryl) or alpha- number of carbon atoms ranges from 0 to 40, or beta- (for alkyl) positions, Biso—(HS—) or optionally having halogen or polarizing or alpha- or beta-(HS—)azo compounds, or water-insolubilizing solubilizing groups Polyo—(HS—) or alpha- or beta-(HS—)azo attached. (Must include ortho-thio, mercapto, or compounds) (N–S Bidentates, N–S hiocarbonyl substituted aryl azo compounds, Tridentates, N-S Tetradentates, or N–S and alpha- or beta-thio, mercapto, or Hexadentates) hiocarbonylalkyl azo compounds.) Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #16: R N=N C(=S)- NR'R' for DiaZeneformothioamides, diazeneformothioamides, and R-N=N-CRR"—C(=S)—NR"R" DiaZeneacetothioamides, or diaZeneacetothioamides, Bis(diazeneformothioamides), where R, R', R", R", and R" represent H, Bis(diazeneacetothioamides), NH2, or any organic functional group wherein Poly(diazeneformothioamides), and he number of carbon atoms ranges from 0 to Poly(diazeneacetothioamides) (N–S 40, optionally having halogen or polarizing or Bidentates, N-S Tetradentates, and N–S water-insolubilizing solubilizing groups Hexadentates) attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #17: R N=N C(=S)- O R' or R N=N-CR'R' C(=S)- O R" DiaZenecarbothioic acids, or diaZenecarbothioic acids, and R-N=N-C(—S)—S-R' DiaZenecarbodithioic acids, or R N=N-CR'R' C(=S)–S-R" Bis(diaZenecarbothioic acids), or diazenecarbodithoic acids, where R, R', Bis(diaZenecarbodithioic acids), R", and R" represent H, NH2, or any organic Poly(diaZenecarbothioic acids), unctional group wherein the number of carbon Poly(diazenecarbodithioic acids) and atoms ranges from 0 to 40, optionally having derivatives thereof (N–S Bidentates, N–S halogen or polarizing or water Tetradentates, N–S Hexadentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #18: R N=N C(=S) R' for Diazeneformothioaldehydes, diazeneformothioaldehydes, and R-N=N–CRR"—C(=S)—R" DiaZeneacetothioaldehydes, O Bis(diazeneformothioaldehydes), diazeneacetothioaldehydes, where R, R', R", US 7,789,958 B2 57 58

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Bis(diazeneacetothioaldehydes), and R" represent H, NH2, or any organic Poly(diazeneformothioaldehydes), and unctional group wherein the number of carbon Poly(diazeneacetothioaldehydes) (N–S atoms ranges from 0 to 40, optionally having Bidentates, N-S Tetradentates and N–S halogen or polarizing or water Hexadentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #19: Diazenediformothioamides, O DiaZenediacetothioamides, diaZenediformothioamides, and Bis(diazenediformothioamides), or RR' N C(=S) CR"R" N=N CR"R" C(=S) NR"R" Bis(diazenediacetothioamides), RR N C(=S) CR"R" N=N CR"R" C(=O) NR"R" Poly(diazenediformothioamides), and or diaZenediacetothioamides, Poly(diazenediacetothioamides) (N–S where R, R', R", R", R", R", R", and Tridentates and N–S Hexadentates) R" represent H, NH, or any organic unctional 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 Patoms. N-S Valence Stabilizer #20: DiaZenedicarbothioic acids, DiaZenedicarbodithioic acids, Bis(diazenedicarbothioic acids), Bis(diazenedicarbodithioic acids), Poly(diazenedicarbothioic acids), Poly(diazenedicarbodithioic acids) and O derivatives thereof (N–S Tridentates and N–S diazenedicarboditholic acids, where R, R', R", Hexadentates) R", R", and R" represent H, NH, 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 Patoms. N-S Valence Stabilizer #21: RC(=S) N=N C(=S) R' or RC(=S) N=N-C(=O) R' Diazenediformothioaldehydes, or diazenediformothioaldehydes, and Diazenediacetothioaldehydes, RC(=S) CR'R'' N N CR"R" C(=S) R" or Bis(diazenediformothioaldehydes), RC(=S) CR'R'' N N CR"R" C(=O) R" for Bis(diazenediacetothioaldehydes), diazenediacetothioaldehydes, where R, R', R", Poly(diazenediformothioaldehydes), and R", R", and R" represent H, NH, or any Poly(diazenediacetothioaldehydes) (N–S organic functional group wherein the number of Tridentates and N–S Hexadentates) 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 Patoms. N-S Valence Stabilizer #22: R N=N CR-N NR"R", where R, R', R", and Ortho-thio (or-mercapto) Substituted R" represent H, or any organic functional Formazans, Bis(o-thio or -mercapto group wherein the number of carbon atoms Substituted formazans), and Poly(o-thio or - ranges from 0 to 40, optionally having halogen mercapto Substituted formazans) (N–S or polarizing or water Bidentates, N-S Tridentates, N–S insolubilizing solubilizing groups attached. Tetradentates, and N–S Hexadentates) (Must include ortho-thio or mercapto substituted aryl R derivatives, and beta-thio or mercapto Substituted alkyl R derivatives.) Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #23: RRC=N N=CR"R" or RR'C=N NR"R" (for Ortho-thio (or-mercapto) Substituted ketazines), where R, R', R", and R" represent Azines (including ketazines), Bis(o-thio or H, or any organic functional group wherein the mercapto Substituted azines), and Poly(o- number of carbon atoms ranges from 0 to 40, thio or mercapto substituted azines) (N–S optionally having halogen or polarizing or Bidentates, N-S Tridentates, N–S water-insolubilizing solubilizing groups Tetradentates, and N–S Hexadentates) attached. (Must include ortho-thio or mercapto substituted aryl R derivatives, and beta-thio or mercapto Substituted alkyl R derivatives.) Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #24: 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 with ortho- or alpha- or beta-thio or number of carbon atoms ranges from 0 to 40, mercapto or thiocarbonyl substitution (N–S optionally having halogen or polarizing or US 7,789,958 B2 59 60

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Bidentates, N-S Tridentates, N–S water-insolubilizing solubilizing groups Tetradentates, N-S Pentadentates, or N–S attached. (Must contain ortho- or alpha- or beta Hexadentates). Also includes Schiff Bases thio or mercapto or thiocarbonyl Substitution.) derived from the reaction of carbonyl Ligand can also contain nonbinding N, O, S, or compounds with dithiocarbazates, and Patoms. hydrazones with ortho-S substitution. N-S Valence Stabilizer #25: RRC. N. R.' N-CR'R' or R N C R. C. N. R. Schiff Bases with two Imine (C=N) Groups or RC–N R' N–CR", where R, R', R", R", and with ortho- or alpha- or beta-thio or and R" represent H, or any organic functional mercapto or thiocarbonyl substitution (N–S group wherein the number of carbon atoms Tridentates, N-S Tetradentates, N–S ranges from 0 to 40, optionally having halogen Pentadentates, or N-S Hexadentates). Also or polarizing or water includes Schiff Bases derived from the insolubilizing solubilizing groups attached. reaction of carbonyl compounds with (Must contain ortho- or alpha- or beta-thio or dithiocarbazates, and hydrazones with mercapto or thiocarbonyl Substitution.) Ligand ortho-S substitution. can also contain nonbinding N, O, S, or P atOnS. N-S Valence Stabilizer #26: N(—R-N=CR'R"), where R, R', and R" Schiff Bases with three Imine (C=N) represent H, or any organic functional group Groups and with ortho- or alpha- or beta- wherein the number of carbon atoms ranges thio or mercapto or thiocarbonyl from 0 to 40, optionally having halogen or Substitution (N-S Tetradentates, N–S polarizing or water-insolubilizing solubilizing Pentadentates, or N-S Hexadentates). Also groups attached. (Must contain ortho- or alpha includes Schiff Bases derived from the or beta-thio or mercapto or thiocarbonyl reaction of carbonyl compounds with Substitution.) Ligand can also contain dithiocarbazates, and hydrazones with nonbinding N, O, S, or Patoms. ortho-S substitution. N-S Valence Stabilizer #27: R-CR'( NR"R"). R" C(- SR")R"R"), Thioalkyl Amines (Aminothiols or R-CR'( NR"R")). R" C(-S-S R")R"R", Aminodisulfides) and Thioalkyl Imines or (R-CR'( NR"R")). R" (C(=S)R"), (Iminothiols or Iminodisulfides) (N–S or thioalkyl Bidentates, N-S Tridentates, N–S amines; and (R-C(=NR)) —R"—C(—SR")R"R", Tetradentates, and N–S Hexadentates) R-C(=NR)). R"—C(-S-SR")R"R"), or (R-C(=NR)-R"—C(=S)R"). or thioalkyl imines, where R, R', R", R", R", R", R", and R" represent H, NH2, or any organic functional group wherein the number of carbon atoms ranges rom 0 to 40, optionally 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 Patoms. N-S Valence Stabilizer #28: R( NR'R'')(- SR"), R( NR'R'')(-S-S R"), Thioaryl Amines and Thioaryl Imines (N–S R(-NR'R'')(-C(=S)R"), R(-NRR"). S, R(-NRR"). R"(-SR"), Bidentates, N-S Tridentates, N–S R(—SR"), R"( NR"R"), Tetradentates, and N–S Hexadentates) R( NR'R").I.S., and R( NR'R").I.R"(C(=S)).R" or thioarylamines; and R(—SR"). NH or R(—SR"). NHNH for hioaryl imines, where R, R', R", and R", 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 = 0–2 and y = 1-4. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #29: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional Sulfur Nitrogen Atoms at least one additional containing Substituents (usually thiols, Sulfur Atom Binding Site not in a Ring (N–S mercaptains, disulfides, or thiocarbonyls) that Bidentates, N-S Tridentates, N–S constitute S binding sites. Can include other Tetradentates, or N-S Hexadentates) 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 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. N-S Valence Stabilizer #30: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional Sulfur US 7,789,958 B2 61 62

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Nitrogen Atoms at least one additional containing Substituents (usually thiols, Sulfur Atom Binding Site not in a Ring (N–S mercaptains, disulfides, or thiocarbonyls) that Bidentates, N-S Tridentates, N–S constitute S binding sites. Can include other Tetradentates, or N-S Hexadentates) 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 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. N-S Valence Stabilizer #31: 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 nitrogen-containing least one additional Nitrogen Atom Binding Substituents (usually amines, imines, or Site not in a Ring (N-S Bidentates, N–S hydrazides) that constitute N binding sites. Can Tridentates, N-S Tetradentates, or N–S include other ring systems bound to the Hexadentates) heterocyclic ring or to the N-containing substituent, but they do not coordinate with the stabilized, high valence metalion. Ring(s) can also contain O, S, or Patoms. This 5-membered 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-S Valence Stabilizer #32: 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 nitrogen-containing least one additional Nitrogen Atom Binding Substituents (usually amines, imines, or Site not in a Ring (N-S Bidentates, N–S hydrazides) that constitute N binding sites. Can Tridentates, N-S Tetradentates, or N–S include other ring systems bound to the Hexadentates) heterocyclic ring or to the N-containing substituent, but they do not coordinate with the stabilized, high valence metalion. Ring(s) can also contain O, S, or Patoms. This 6-membered 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-S Valence Stabilizer #33: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional Sulfur Nitrogen Atoms at least one additional containing rings that constitute S binding sites. Sulfur Atom Binding Site in a Separate Can include other ring systems bound to the N Ring (N-S Bidentates, N–S Tridentates, N–S or S-containing heterocyclic rings, but they do Tetradentates) 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 additional S-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. N-S Valence Stabilizer #34: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional Sulfur Nitrogen Atoms at least one additional containing rings that constitute S binding sites. Sulfur Atom Binding Site in a Separate Can include other ring systems bound to the N Ring (N-S Bidentates, N–S Tridentates, N–S or S-containing heterocyclic rings, but they do Tetradentates) 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 additional S-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. N-S Valence Stabilizer #35: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, Six-, Eight-, and Ten six, eight, or ten binding sites composed of Membered Macrocyclics, Macrobicyclics, nitrogen and Sulfur to valence stabilize the and Macropolycyclics (including central metalion. Can include other Catapinands, Cryptands, Cyclidenes, and hydrocarbon or ring systems bound to this Sepulchrates) wherein all Binding Sites are macrocyclic ligand, but they do not coordinate composed of Nitrogen (usually amine or with the stabilized, high valence metal ion. This imine groups) or Sulfur (usually thiols, ligand and/or attached, uncoordinating US 7,789,958 B2 63 64

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation mercaptains, or thiocarbonyls) and are not hydrocarbons rings may or may not have contained in Component Heterocyclic halogen or polarizing or water Rings (N-S Bidentates, N–S Tridentates, N–S insolubilizing solubilizing groups attached. Tetradentates, and N–S Hexadentates) N-S Valence Stabilizer #36: Macrocyclic ligands containing a total of four, Four-, Six-, Eight-, or Ten-Membered six, eight, or ten heterocyclic rings containing Macrocyclics, Macrobicyclics, and nitrogen or Sulfur binding sites. Can include Macropolycyclics (including Catapinands, other hydrocarbonfring 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 or Sulfur and are contained in ligand and/or attached, uncoordinating Component Heterocyclic Rings (N–S hydrocarbon rings may or may not have halogen Bidentates, N-S Tridentates, N–S or polarizing or water-insolubilizing groups Tetradentates, or N-S Hexadentates) attached. N-S Valence Stabilizer #37: Macrocyclic ligands containing at least one Four-, Six-, Eight-, or Ten-Membered heterocyclic ring. These heterocyclic rings Macrocyclics, Macrobicyclics, and provide nitrogen or Sulfur binding sites to Macropolycyclics (including Catapinands, valence stabilize the central metalion. 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 four, six, eight, or ten. Can Amine, Imine, Thiol, Mercapto, or include other hydrocarbon ring systems bound Thiocarbonyl Groups (N-S Bidentates, N–S to this macrocyclic ligand, but they do not Tridentates, N-S Tetradentates, or N–S coordinate with the stabilized, high valence Hexadentates) 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: R' N(-OH)—C(—R)—2N-R", where R, R', and R" N-Hydroxy(or N,N'-dihydroxy)amidines represent H or any organic functional group and N-Hydroxy(or N,N'- wherein the number of carbon atoms ranges dihydroxy)diamidines (N-O Bidentates, N-O rom 0 to 40, optionally having halogen or Tridentates, or N O Tetradentates) polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #2: RR N C(-NH) NR" CO NR"R" for Guanylureas, Guanidinoureas, guanylureas, and RR' N. C(=NH)– NR" NH CO. NR"R" Bis(guanylureas), Bis(guanidinoureas), or guanidinoureas, where R, R', R", Poly(guanylureas), and R", and R" represent H, NH, or any organic Poly(guanidinoureas) (N-O Bidentates and unctional group wherein the number of carbon N-O 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 Patoms. N-O Valence Stabilizer #3: RR' N C(=NH)– NR" CO-R" for N Amidinoamides, Guanidinoamides, amidinoamides, or RR' N C(=NH) CR"R" CO. N. R"R" Bis(amidinoamides), Bis(guanidinoamides), or 2-amidinoacetamides, and Poly(amidinoamides), and RR' N C(=NH)– NR" NH CO. R" for Poly(guanidinoamides) (including both N guanidinoamides, where R, R', R", R", R", amidinoamides and 2-amidinoacetamides) and R" represent H, NH, or any organic (N-O Bidentates and N-O Tetradentates) unctional 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 Patoms. N-O Valence Stabilizer #4: R C(=NH)– NR' CO R", where R, R', and R", Imidoylamides, Bis(imidoylamides), and represent H or any organic functional group Poly(imidoylamides) (N-O Bidentates and wherein the number of carbon atoms ranges N-O Tetradentates) rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #5: RR' N C(=NH)- O CO. NR"R", where R, R', O-Amidinocarbamates, Bis(O- R", and R" represent H, NH2, or any organic amidinocarbamates), and Poly(O- unctional group wherein the number of carbon amidinocarbamates) (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 Patoms. US 7,789,958 B2 65 66

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation N-O Valence Stabilizer #6: RR' N C(=NH)–S CO NR"R", where R, R', S-Amidinothiocarbamates, Bis(S- R", and R" represent H, NH, or any organic amidinothiocarbamates), and Poly(S- functional group wherein the number of carbon amidinothiocarbamates) (N-O Bidentates atoms ranges from 0 to 40, optionally having and N-O Tetradentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #7: (NH=)(NH=)P(OR)(OR), where R, R', and R" Diimidosulfuric Acid, Bis(diimidosulfuric represent H, NH2, or any organic functional acid), and derivatives thereof (N-O group wherein the number of carbon atoms Bidentates and N-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 Patoms. N-O Valence Stabilizer #8: (NH=)P(-OR)(-OR)(-OR"), where R, R', and Phosphorimidic Acid, Bis(phosphorimidic R" represent H, NH2, or any organic functional acid); and Poly(phosphorimidic acid), and group wherein the number of carbon atoms derivatives thereof (N-O Bidentates) 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 Patoms. N-O Valence Stabilizer #9: (O-)P( NRR')( NR"R") ( NR"R"), where R, Phosphoric Triamides, Bis(phosphoric R", R", R", R", and R" represent H, NH, or triamides), and Poly(phosphoric triamides) any organic functional group wherein the (N-O Bidentates and N-O Tetradentates) 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 Patoms. N-O Valence Stabilizer #10: (O-)P( NRR") ( OR") ( OR") for Phosphoramidic Acid, Phosphorodiamidic Acid, Bis(phosphoramidic acid), for phosphorodiamidic acid, Bis(phosphorodiamidic acid), where R, R', R", R", and R" represent H, Poly(phosphoramidic acid), NH2, or any organic functional group wherein Poly(phosphorodiamidic acid), and the number of carbon atoms ranges from 0 to derivatives thereof (N-O Bidentates and N—O 40, optionally having halogen or polarizing or Tetradentates) water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #11: R' C(=O)—N=C(—R)(-NHR"), where R is an N-Acyl 7-Aminobenzylidenimines (N-O aromatic derivative (i.e. —CHs), and R' and R" Bidentates or N-O Tetradentates) 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. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #12: R C(=NOH) R' for oximes, and R C(=NOH) C(=NOH) R' Oximes, Dioximes, and Poly(oximes) (N-O for dioximes, where Rand R' Bidentates, N-O Tridentates, and N-O represent H, NH2, or any organic functional 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 Patoms. N-O Valence Stabilizer #13: R C(=O) C(=NOH) R', where R and R' Carbonyl oximes, Bis(carbonyl oximes), represent H, NH, or any organic functional and Poly(carbonyl oximes) (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 Patoms. N-O Valence Stabilizer #14: R—C(=N-R")—C(=NOH)—R', where R, R', and Imine oximes, Bis(imine oximes), and R" represent H, NH2, or any organic functional Poly(imine oximes) (including 2-nitrogen group wherein the number of carbon atoms heterocyclic oximes) (N-O Bidentates, N-O ranges from 0 to 40, optionally having halogen Tridentates, N. O Tetradentates, and N-O or polarizing or water US 7,789,958 B2 67 68

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Hexadentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #15: R-CH(-OH)–C(=NOH) R', where R, R', and R" Hydroxy Oximes, Bis(hydroxy oximes), and represent H, NH2, or any organic functional Poly(hydroxy Oximes) (including 2-oxygen group wherein the number of carbon atoms heterocyclic oximes) (N-O Bidentates, N-O ranges from 0 to 40, optionally having halogen Tridentates, N. O Tetradentates, and N-O or polarizing or water Hexadentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #16: RR' C(-NH R") C(=NOH) R", where R, R', Amino oximes, Bis(amino oximes), and R", and R" represent H, NH, or any organic Poly(amino oximes) (N-O Bidentates, N-O functional group wherein the number of carbon Tridentates, N. O Tetradentates, and N-O atoms ranges from 0 to 40, optionally having Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #17: RR' N C(=NOH) R", where R, R', and R' Amido oximes, Bis(amido oximes), and represent H, NH, or any organic functional Poly(amido oximes) (N-O Bidentates, N-O group wherein the number of carbon atoms Tridentates, N. O Tetradentates, and N-O ranges from 0 to 40, optionally having halogen Hexadentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #18: R N=N C(=NOH) R' or RR'C=N NR" R", AZO Oximes, Bis(aZO Oximes), and Poly(aZo where R, R', R", and R" Oximes) (N-O Bidentates, N-O Tridentates, represent H, NH2, or any organic functional N-O Tetradentates, and N—O Hexadentates). group wherein the number of carbon atoms Also includes hydrazone oximes. ranges from 0 to 40, optionally having halogen or polarizing or water insolubilizing solubilizing groups attached. (R is typically an aryl group.) Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #19: o-(ON-) (HO-)Ar, where Arrepresents an 2-Nitrosophenols (o-Quinone monoximes) aromatic group or heterocyclic wherein the (N-O 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 Patoms. N-O Valence Stabilizer #20: o-(ON )(HO—)Ar, where Arrepresents an 2-Nitrophenols (N-O Bidentates) 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 Patoms. N-O Valence Stabilizer #21: R C(=O)- NR’ OH or R C(-OH)=N OH, where Hydroxamates (Hydroxylamines), RandR' represent H, NH, or any organic Bis(hydroxamates), and unctional group wherein the number of carbon Poly(hydroxamates) (N-O Bidentates, N-O atoms ranges from 0 to 40, optionally having Tetradentates, and N—O Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #22: R-N(-NO)—OH, where R represents any organic N-Nitrosohydroxylamines, Bis(N- unctional group wherein the number of carbon nitrosohydroxylamines), and Poly(N- atoms ranges from 1 to 40, optionally having nitrosohydroxylamines) (N-O Bidentates, halogen or polarizing or water N-O Tetradentates, and N—O Hexadentates) insolubilizing solubilizing groups attached. (R is typically an aryl or heterocyclic group.) Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #23: R-CH(-NHR')—C(=O)(-OH) for amino acids and Amino Acids and ortho-Aminocarboxylic ortho-aminocarboxylic acids, and Acids, Peptides, Polypeptides, and Proteins R-CH( NHR') C(=O) (NR" N-O Bidentates, N-O Tridentates, and N-O or peptides, where R, R', R", and R" represent Tetradentates; possibly S-O dentates for any organic functional group wherein the Sulfur-contg. examples such as number of carbon atoms ranges from 1 to 40, penicillamine and cystine optionally having halogen or polarizing or water-insolubilizing solubilizing groups US 7,789,958 B2 69 70

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #24: RCONR'R'', where R, R', and R" represent H, Amides, Bis(amides), and Poly(amides), NH2, or any organic functional group wherein including lactams (N-O Bidentates, N-O the number of carbon atoms ranges from 0 to Tridentates, and N O Tetradentates) 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #25: RR' N C(=O) NR" N=CR"R", where R, R', Semicarbazones, Bis(semicarbazones), and R", R", and R" represent H, or any organic Poly(semicarbazones) (N-O Bidentates, N-O unctional group wherein the number of carbon Tetradentates, and N—O Hexadentates) 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 Patoms. N-O Valence Stabilizer #26: R C(=O)- NR' N=CR"R", where R, R', R", and Acyl hydrazones, Bis(acylhydrazones), and R" represent H, or any organic functional Poly(acyl hydrazones) (N-O Bidentates, N-O group wherein the number of carbon atoms Tetradentates, and N—O Hexadentates) 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 Patoms. N-O Valence Stabilizer #27: R N=N C(=O) NR' N R"R", where R, R', R", Carbazones (DiaZenecarboxylic and R" represent H, or any organic functional hydrazides), Bis(carbazones), and group wherein the number of carbon atoms Poly(carbazones) (N-O Bidentates, N-O ranges from 0 to 40, optionally having halogen Tetradentates, and N—O Hexadentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #28: R-N=N-R' for azo compounds, R N=N. NH-R' AZO compounds including triaZenes with for triaZenes, where R, and R' represent Hor hydroxyl or carboxy or carbonyl any organic functional group wherein the Substitution at the ortho- (for aryl) or alpha number of carbon atoms ranges from 0 to 40, or beta- (for alkyl) positions, Biso-(HO-) optionally having halogen or polarizing or or alpha- or beta-(HO—)azo compounds, or water-insolubilizing solubilizing groups Polyo-(HO-) or alpha- or beta-(HO-)azo attached. (Must include ortho-hydroxy or compounds) (N-O Bidentates, N-O carboxy or carbonyl Substituted arylazo Tridentates, N. O Tetradentates, or N- O compounds, and alpha- or beta-hydroxy or Hexadentates) carboxy or carbonyl alkyl azo compounds.) Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #29: R-N=N-C(=O)—NR'R" for diazeneformamides, DiaZeneformamides, DiaZeneacetamides, and R N=N CR'R' C(=O)- NR"R" for Bis(diazeneformamides), diazeneacetamides, where R. R. R", R", and Bis(diazeneacetamides), R" represent H, NH2, or any organic functional Poly(diazeneformamides), and group wherein the number of carbon atoms Poly(diazeneacetamides) (N-O Bidentates, ranges from 0 to 40, optionally having halogen N-O Tetradentates, and N—O Hexadentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #30: R-N=N-C(=O)—O—R' for diazeneformic acid, DiaZeneformic acids, DiaZeneacetic acids, and R N=N CR'R' C(=O)-O-R" for Bis(diazeneformic acids), Bis(diazeneacetic diazeneacetic acid, where R. R. R", and R" acids), Poly(diazeneformic acids), represent H, NH, or any organic functional Poly(diazeneacetic acids), and derivatives group wherein the number of carbon atoms thereof (N-O Bidentates, N-O ranges from 0 to 40, optionally having halogen Tetradentates, N-O Hexadentates) or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #31: R-N=N-C(=O)—R' for diazeneformaldehydes, Diazeneformaldehydes, and R N=N CR'R' C(=O)-R" for DiaZeneacetaldehydes, diazeneacetaldehydes, where R, R', R", and R" Bis(diazeneformaldehydes), represent H, NH2, or any organic functional Bis(diazeneacetaldehydes), group wherein the number of carbon atoms Poly(diazeneformaldehydes), and ranges from 0 to 40, optionally having halogen Poly(diazeneacetaldehydes) (N-O or polarizing or water Bidentates, N- O Tetradentates and N O insolubilizing solubilizing groups attached. US 7,789,958 B2 71 72

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Hexadentates) Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #32: DiaZenediformamides, diazenediformamides, and RR' N–C(=O)—CR"R" DiaZenediacetamides, for diazenediacetamides, where R, R', R", R", Bis(diazenediformamides), R", R", R", and R" represent H, NH, Bis(diazenediacetamides), or any organic functional group wherein the Poly(diazenediformamides), and number of carbon atoms ranges from 0 to 40, Poly(diazenediacetamides) (N-O optionally having halogen or polarizing or Tridentates and N—O Hexadentates) water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, N-O Valence Stabilizer #33: DiaZenediformic acids, DiaZenediacetic diazenediformic acid, and R-O-C(=O)—CR'R'" N. N. acids, Bis(diazenediformic acids), O Bis(diazenediacetic acids), diazenediacetic acid, where R, R', R", R", R", Poly(diazenediformic acids), and R" represent H, NH, or any organic Poly(diazenediacetic acids) and derivatives unctional group wherein the number of carbon thereof (N-O Tridentates and N—O atoms ranges from 0 to 40, optionally having Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #34: RC(=O)- N=N C(=O) R' for Diazenediformaldehydes, diazenediformaldehydes, and RC(=O)—CR"R" DiaZenediacetaldehydes, O Bis(diazenediformaldehydes), diazenediacetaldehydes, where R, R, R", R", Bis(diazenediacetaldehydes), R", and R" represent H, NH, or any organic Poly(diazenediformaldehydes), and unctional group wherein the number of carbon Poly(diazenediacetaldehydes) (N-O atoms ranges from 0 to 40, optionally having Tridentates and N—O Hexadentates) halogen or polarizing or water insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #35: R N=N CR' N NR"R", where R, R', R", and Ortho-hydroxy (or -carboxy) Substituted R" represent H, or any organic functional Formazans, Bis(O-hydroxy or -carboxy group wherein the number of carbon atoms Substituted formazans), and Poly(o-hydroxy ranges from 0 to 40, optionally having halogen or -carboxy substituted formazans) (N-O or polarizing or water Bidentates, N-O Tridentates, N- O insolubilizing solubilizing groups attached. Tetradentates, and N—O Hexadentates) (Must include ortho-hydroxy or carboxy substituted aryl R derivatives, and beta-hydroxy or carboxy substituted alkyl Riderivatives.) Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #36: Ortho-hydroxy (or -carboxy) Substituted ketazines), where R, R', R", and R" represent Azines (including ketazines), Bis(O- H, or any organic functional group wherein the hydroxy or carboxy Substituted azines), and number of carbon atoms ranges from 0 to 40, Poly(o-hydroxy or carboxy substituted optionally having halogen or polarizing or azines) (N-O Bidentates, N-O Tridentates, water-insolubilizing solubilizing groups N-O Tetradentates, and N—O Hexadentates) attached. (Must include ortho-hydroxy or carboxy substituted aryl R derivatives, and beta hydroxy or carboxy substituted alkyl R derivatives.) Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #37: 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 with ortho- or alpha- or beta-hydroxy number of carbon atoms ranges from 0 to 40, or carboxy or carbonyl substitution (N-O optionally having halogen or polarizing or Bidentates, N-O Tridentates, N- O water-insolubilizing solubilizing groups Tetradentates, N-O Pentadentates, or N- O attached. (Must contain ortho- or alpha- or beta Hexadentates). Also includes hydrazones hydroxy or carboxy or carbonyl Substitution.) with ortho-O substitution. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #38: RRC. N. R.' N-CR'R' or R N C R. C. N. R. Schiff Bases with two Imine (C=N) Groups and with ortho- or alpha- or beta-hydroxy and R" represent H, or any organic functional or carboxy or carbonyl substitution (N-O group wherein the number of carbon atoms Tridentates, N. O Tetradentates, N. O ranges from 0 to 40, optionally having halogen Pentadentates, or N-O Hexadentates). Also or polarizing or water includes hydrazones with ortho-O insolubilizing solubilizing groups attached. Substitution. (Must contain ortho- or alpha- or beta-hydroxy or carboxy or carbonyl Substitution.) Ligand US 7,789,958 B2 73 74

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation can also contain nonbinding N, O, S, or P atOnS. N-O Valence Stabilizer #39: N(—R-N=CR'R"), where R, R', and R" Schiff Bases with three Imine (C=N) represent H, or any organic functional group Groups and with ortho- or alpha- or beta wherein the number of carbon atoms ranges hydroxy or carboxy or carbonyl substitution from 0 to 40, optionally having halogen or (N-O Tetradentates, N-O Pentadentates, or polarizing or water-insolubilizing solubilizing N-O Hexadentates). Also includes groups attached. (Must contain ortho- or alpha hydrazones with ortho-O substitution. or beta-hydroxy or carboxy or carbonyl Substitution.) Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #40: (R-C(NR'R")). R"—Si(-OR").R"), where Sillylaminoalcohols (N-O Bidentates, N-O R, R', R", R", and R" represent H, NH, or Tridentates, N. O Tetradentates, and N-O any organic functional group wherein the Hexadentates) number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached, and X and y = 1-6, Z = 1-3. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #41: R-C(=NR)). R"—IC OR")R"R"), or (R-C(=NR)-R" (C(=O)R"), Hydroxyalkyl Imines (Imino Alcohols) (N-O where R, R', R", Bidentates, N-O Tridentates, N- O R", R", and R" represent H, NH, or any Tetradentates, and N—O Hexadentates) 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 and y = 1-6. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #42: R( NR'R")(-OR"), R( NR'R'')(-C(=O)R"), Hydroxyaryl Amines and Hydroxyaryl R( NR'R").I.O. (R( NR'R"), sR"( OR"), Imines (N-O Bidentates, N-O Tridentates, R(-OR), I-R"( NR"R"), and R( NRR").R"(C(=O)),R" N-O Tetradentates, and N—O Hexadentates) or hydroxyaryl amines; and R(-OR). NH or R(-OR). NHNH or hydroxyaryl imines, where R. R', R", R", and R" represent H, NH, 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 = 0–2 and y = 1-4. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #43: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional oxygen Nitrogen Atoms at least one additional containing Substituents (usually hydroxy, Oxygen Atom Binding Site not in a Ring carboxy or carbonyl groups) that constitute O (N-O Bidentates, N-O Tridentates, N-O binding sites. Can include other ring systems Tetradentates, or N-O Hexadentates) 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 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. N-O Valence Stabilizer #44: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional oxygen Nitrogen Atoms at least one additional containing Substituents (usually hydroxy, Oxygen Atom Binding Site not in a Ring carboxy, or carbonyl groups) that constitute O (N-O Bidentates, N-O Tridentates, N-O binding sites. Can include other ring systems Tetradentates, or N-O Hexadentates) 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 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. N-O Valence Stabilizer #45: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one or two oxygen atoms. In addition, ligand containing One or Two Oxygen Atoms at contains additional nitrogen-containing US 7,789,958 B2 75 76

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation least one additional Nitrogen Atom Binding Substituents (usually amines, imines, or Site not in a Ring (N-O Bidentates, N-O hydrazides) that constitute N binding sites. Can Tridentates, N. O Tetradentates, or N- O include other ring systems bound to the Hexadentates) heterocyclic ring or to the N-containing substituent, but they do not coordinate with the stabilized, high valence metalion. Ring(s) can also contain O, S, or Patoms. This 5-membered 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-O Valence Stabilizer #46: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one or two oxygen atoms. In addition, ligand containing One or Two Oxygen Atoms at contains additional nitrogen-containing least one additional Nitrogen Atom Binding Substituents (usually amines, imines, or Site not in a Ring (N-O Bidentates, N-O hydrazides) that constitute N binding sites. Can Tridentates, N. O Tetradentates, or N- O include other ring systems bound to the Hexadentates) heterocyclic ring or to the N-containing substituent, but they do not coordinate with the stabilized, high valence metalion. Ring(s) can also contain O, S, or Patoms. This 6-membered 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-O Valence Stabilizer #47: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional oxygen Nitrogen Atoms at least one additional containing rings that constitute Obinding sites. Oxygen Atom Binding Site in a Separate Can include other ring systems bound to the N Ring (N-O Bidentates, N-O Tridentates, N-O or O-containing heterocyclic rings, but they do Tetradentates) 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 additional O-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. N-O Valence Stabilizer #48: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, three, or four nitrogen atoms. In containing One, Two, Three, or Four addition, ligand contains additional oxygen Nitrogen Atoms at least one additional containing rings that constitute Obinding sites. Oxygen Atom Binding Site in a Separate Can include other ring systems bound to the N Ring (N-O Bidentates, N-O Tridentates, N-O or O-containing heterocyclic rings, but they do Tetradentates) 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 additional O-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. N-O Valence Stabilizer #49: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, Six-, Eight-, and Ten six, eight, or ten binding sites composed of Membered Macrocyclics, Macrobicyclics, nitrogen and oxygen to valence stabilize the and Macropolycyclics (including central metalion. Can include other Catapinands, Cryptands, Cyclidenes, and hydrocarbon or ring systems bound to this Sepulchrates) wherein all Binding Sites are macrocyclic ligand, but they do not coordinate composed of Nitrogen (usually amine or with the stabilized, high valence metal ion. This imine groups) or Oxygen (usually hydroxy, ligand and/or attached, uncoordinating carboxy, or carbonyl groupSS) and are not hydrocarbons rings may or may not have contained in Component Heterocyclic halogen or polarizing or water Rings (N-O Bidentates, N-O Tridentates, insolubilizing solubilizing groups attached. N-O Tetradentates, and N—O Hexadentates) N-O Valence Stabilizer #50: Macrocyclic ligands containing a total of four, Four-, Six-, Eight-, or Ten-Membered six, eight, or ten heterocyclic rings containing Macrocyclics, Macrobicyclics, and nitrogen or oxygen binding sites. Can include Macropolycyclics (including Catapinands, other hydrocarbonfring 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 or Oxygen and are contained in ligand and/or attached, uncoordinating Component Heterocyclic Rings (N-O hydrocarbon rings may or may not have halogen Bidentates, N-O Tridentates, N- O or polarizing or water-insolubilizing groups Tetradentates, or N-O Hexadentates) attached. N-O Valence Stabilizer #51: Macrocyclic ligands containing at least one US 7,789,958 B2 77 78

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Four-, Six-, Eight-, or Ten-Membered heterocyclic ring. These heterocyclic rings Macrocyclics, Macrobicyclics, and provide nitrogen or oxygen binding sites to Macropolycyclics (including Catapinands, valence stabilize the central metalion. 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 four, six, eight, or ten. Can Amine, Imine, Hydroxy, Carboxy, or include other hydrocarbon ring systems bound Carbonyl Groups (N-O Bidentates, N-O to this macrocyclic ligand, but they do not Tridentates, N. O Tetradentates, or N- O coordinate with the stabilized, high valence 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 #1: R C(=S) CR'R' C(=O) R" where R, R', R", 1,3-Monothioketones (Monothio-beta and R" represent H, NH2, or any organic ketonates), 1,3,5-Monothioketones, 1,3,5- functional group wherein the number of carbon Dithioketones, Bis(1,3-Monothioketones), atoms ranges from 0 to 40, optionally having and Poly(1,3-Monothioketones) (S-O halogen or polarizing or water Bidentates, S. O Tridentates, S- O insolubilizing solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. S OValence Stabilizer #2: RR N C(=S) CR"R" C(=O) N. R"R" Thiomalonamides (Thiomalonodiamides), where R, R', R", R", R", and R" represent H, Bis(thiomalonamides), and NH2, or any organic functional group wherein Polythiomalonamides (S-O Bidentates, S-O the number of carbon atoms ranges from 0 to Tridentates, S. O Tetradentates) 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. S OValence Stabilizer #3: RR' N C(=O) CR"R" C(=S)-R" for 2 2-Thioacylacetamides, 2 hioacylacetamides, and RR' N–C(=S)—CR"R" C(=O)—R" Acylthioacetamides, Bis(2- or 2-acylthioacetamides, where R, thioacylacetamides), R", R", R", and R" represent H, NH, or any Bis(2acylthioacetamides), Poly(2- organic functional group wherein the number of thioacylacetamides), and Poly(2- carbon atoms ranges from 0 to 40, optionally Acylthioacetamides) (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 Patoms. S O Valence Stabilizer #4: RR' N C(=S)–S C(=O)- N R"R" where R, R', Dithiodicarbonic Diamides, R", and R" represent H, NH2 or any organic Bis(dithiodicarbonic diamides), and unctional group wherein the number of carbon Poly(dithiodicarbonic diamides) (S-O atoms ranges from 0 to 40, optionally having Bidentates, S. O Tridentates, S- O halogen or polarizing or water Tetradentates) insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. S OValence Stabilizer #5: (R-O-)(R'—O-)P(=S)—P(=O)(-O-R")(-O-R"); Monothiohypophosphoric Acids, (R-O-)(R'—S—)P(=S)—P(=O)(—S—R")(-O-R"); or Bis(monothiohypophosphoric acids), and (R-S–)(R'—S—)P(=S)—P(=O)(—S—R") (—S—R"), Poly(monothiohypophosphoric acids), and where R, R', R", and R" represent H, NH, or derivatives thereof (S—O Bidentates, S-O any organic functional group wherein the Tridentates, S. O Tetradentates) 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 Patoms. 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 OValence Stabilizer #6: Monothiohypophosphoramides, where R, R', R", R", Bis(monothiohypophosphoramides), and R", R", R", and R" represent H, NH, or Poly(monothiohypophosphoramides) (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 Patoms. Note: these ligands are not to be confused with hypophosphorous acid derivatives (hypophosphites) (R—O—) US 7,789,958 B2 79 80

TABLE 4-continued Wide Band Organic Valence Stabilizers for the Mn' and Mn' Ions

General Structural Name (Type of Organic) Structural Representation R"R"P(=O) which are very reducing and therefore unacceptable for stabilization of high valence states in metal ions. S OValence Stabilizer #7: (R-O-)(R'—O-)P(=S)—NH-P(=O)(-O-R")(-O-R"); Monothioimidodiphosphoric Acids, (R-O-)(R'—S—)P(=S)—NH-P(=O)(—S—R") ( O—R"); Monothiohydrazidodiphosphoric Acids, or (R-S )(R'—S—)P(—S)—NH-P(=O)(—S—R")(—S—R") Bis(monothioimidodiphosphoric Acids), or monothioimidodiphosphoric Bis(monothiohydrazidodiphosphoric acids, and - NH-NH-derivatives for Acids), Poly(monothioimidodiphosphoric monothiohydrazidodiphosphoric acids, where Acid), R. R', R", and R" represent H, NH2 or any Poly(monothiohydrazidodiphosphoric 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 Patoms. S OValence Stabilizer #8: (RR' N )(R"R" N )P(=S) NH P(=O)( N R"R") ( N R"R") Monothioimidodiphosphoramides, O Monothiohydrazidodiphosphoramides, monothioimidodiphosphoramides, and —NH-NH Bis(monothioimidodiphosphoramides), derivatives for Bis(monothiohydrazidodiphosphoramides), monothiohydrazidodiphosphoramides, where R, Poly(monothioimidodiphosphoramides), R", R", R", R", R", R", and R" and represent H, NH2 or any organic functional Poly(monothiohydrazidodiphosphoramides) group wherein the number of carbon atoms (S—O 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 Patoms. S OValence Stabilizer #9: (RR' N )(R"R" N )P(=S) S P(=O)( N R"R") ( N R"R"), Monothiodiphosphoramides, or (RR N )(R"R" N )P(=S) O P(=O)( N R"R") ( N R"R"), Bis(monothioiphosphoramides), and where R, R', R", R", R", R", Poly(monothiodiphosphoramides) (S-O R", and R" represent H, NH, or any Bidentates, S. O Tridentates, S- O organic functional group wherein the number of 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 Patoms. S OValence Stabilizer #10: (R-O-)(R'—O-)P(=S)—O—P(=O)(-O-R")(-O-R"); Monothiodiphosphoric Acids, (R-O-)(R'—O-)P(=S)—S—P(=O)(-O-R")(-O-R"); Bis(monothioiphosphoric Acids), (R-O-)(R'—S—)P(=S)—O—P(=O)(—S—R") ( O—R"); Poly(monothiodiphosphoric Acids), and (R-O-)(R'—S—)P(=S)—S—P(=O)(—S—R")(-O-R"); derivatives thereof (S—O Bidentates, S-O or (R-S )(R'—S—)P(—S)—S—P(=O)(—S—R")(—S—R"), Tridentates, S. O Tetradentates) where R, R', R", R", R", R", R", and R" represent H, NH2 or any organic unctional 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 Patoms. S OValence Stabilizer #11: RR'N'=C(OH)(SH), where R and R' represent Monothiocarbamates, H, OH, SH, OR" (R"—C-Co alkyl or aryl), SR" Bis(monothiocarbamates), and (R'=C-Co alkyl or aryl), NH2 or any organic Poly(monothiocarbamates) (including N- unctional group wherein the number of carbon hydroxymonothiocarbamates and N- atoms ranges from 0 to 40, optionally having mercaptomonothiocarbamates) (S—O halogen or polarizing or water Bidentates, S. O Tridentates, and S- O insolubilizing solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. Miscellaneous Valence Stabilizer #1: Hydroxo and OXO ligands bound directly to the Hydroxo and OXO Ligands high valence metalion. US 7,789,958 B2 81 82 NValence Stabilizer #1: Examples of monoamines (N mono ethyl-1,3-propanediamine (tam); 1.2.3,4-tetraminobutane dentates) that meet the requirements for use as “wide band' (tab); N,N'-(2-aminophenyl)-1,2-ethanediamine; and N,N'- valence stabilizers for Mn" and/or Mn" include, but are not (2-aminophenyl)-1,3-propanediamine. limited to: ammonia; ethylamine; n-dodecylamine; octy lamine; phenylamine; cyclohexylamine; diethylamine; dio N Valence Stabilizer #5. Examples of pentamines (N N ctylamine; diphenylamine; dicyclohexylamine; azetidine; bidentates, N N tridentates, or N N tetradentates) that hexamethylenetetramine (Urotropin); aziridine; azepine; meet the requirements for use as “wide band valence stabi pyrrolidine; benzopyrrolidine: dibenzopyrrolidine; naphtho lizers for Mn" and/or Mn" include, but are not limited to: pyrrolidine; piperidine; benzopiperidine, dibenzopiperidine; N—N-(2-aminoethyl)-2-aminoethyl-N'-(2-aminoethyl)-1, 10 2-ethanediamine (2.2.2.2-pent, tetren); N-N-(3-aminopro naphthopiperidine, azacycloheptane (hexamethyleneimine); pyl)-2-aminoethyl-N'-(3-aminopropyl)-1,2-ethanediamine aminonorbornane; adamantanamine; aniline; benzylamine; (3.2.2,3-pent); N-N-(3-aminopropyl)-3-aminopropyl)-N'- toluidine; phenethylamine; Xylidine; cumidine; naphthy (3-aminopropyl)-1,3-propanediamine (3,3,3,3-pent, caldo lamine; polyalkylamines; polyanilines; and fluorenediamine. pentamine); N-N-(2-aminobenzyl)-2-aminoethyl-N'-(2- NValence Stabilizer #2: Examples of diamines (N N biden 15 aminopropyl)-1,2-ethanediamine; N-N-(2-aminoethyl)-2- tates) that meet the requirements for use as “wide band aminoethyl-N,N-(2-aminoethyl)amine (trenen); and valence stabilizers for Mn" and/or Mn' include, but are not N—N-(2-aminopropyl)-2-aminoethyl-N,N-(2-aminoet limited to: hydrazine; phenylhydrazine; 1,1-diphenylhydra hyl)amine (4-Me-trenen). Zine; 1,2-diphenylhydrazine (hydrazobenzene); methanedi amine; ethylenediamine (1.2-ethanediamine, en); trimethyl N Valence Stabilizer #6: Examples of hexamines (N N enediamine (1,3-propanediamine); putrescine (1,4- bidentates, N N tridentates, N N tetradentates, or butanediamine); cadaverine (1.5-pentanediamine); N N N N N N hexadentates) that meet the require hexamethylenediamine (1.6-hexanediamine); 2.3-diami ments for use as “wide band valence stabilizers for Mn" nobutane; stilbenediamine (1,2-diphenyl-1,2-ethanedi and/or Mn" include, but are not limited to: N,N'-N-(2-ami amine); cyclohexane-1,2-diamine; cyclopentane-1,2-di 25 noethyl)-2-aminoethyl-1,2-ethanediamine (2.2.2.2.2-hex, amine; 1,3-diazacyclopentane; 1,3-diazacyclohexane: linpen); N,N'-N-(2-aminoethyl)-3-aminopropyl-1,2- piperazine; benzopiperazine: dibenzopiperazine; naphtho ethanediamine (2.3.2.3.2-hex); N.N.N',N'-(2-aminoethyl)-1, piperazine; diazepine; thiadiazepine; Oxodiazepine; Sparteine 2-ethanediamine (penten, ten); N.N.N',N'-(2-aminoethyl)-1- (lupinidine): 2-(aminomethyl)azacyclohexane: 2-(aminom methyl-1,2-ethanediamine (tpin, R-5-Me-penten); N.N.N',N'- ethyl)piperidine: 2-(aminomethyl)pyrrolidine: 2-(aminom 30 (2-aminoethyl)-1,3-propanediamine (ttn); N.N.N',N'-(2- ethyl)aZetidine: 2-(2-aminoethyl)aziridine; 1,2-diaminoben aminoethyl)-1,4-butanediamine (tbn); N,N,N',N'-(2- Zene; benzidine; bis(2,2'-piperazino)-1,2-ethene; 1,4- aminoethyl)-1,3-dimethyl-1,3-propanediamine (R.R-tptn, diazabicyclo[2.2.2]octane; naphthylethylenediamine; and R.S-tptn); N-(2-aminoethyl)-2.2-N-(2-aminoethyl)ami 1.2-dianilinoethane. nomethyl-1-propaneamine (sen); and N-(3-aminopropyl)-2, NValence Stabilizer #3: Examples of triamines (N N biden 35 2-N-(3-aminopropyl)aminomethyl-1-propaneamine (stn). tates or N N tridentates) that meet the requirements for use as “wide band' valence stabilizers for Mn" and/or Mn" NValence Stabilizer #7a: Examples of 5-membered hetero include, but are not limited to: N-(2-aminoethyl)-1,2- cyclic rings containing one nitrogen atom (N monodentates) ethanediamine (dien, 2.2-tri); N-(2-aminoethyl)-1,3-pro that meet the requirements for use as “wide band valence panediamine (2,3-tri); N-(3aminopropyl)-1,3-propanedi 40 stabilizers for Mn" and/or Mn" include, but are not limited amine (3,3-tri, dipt); N-(3-aminopropyl)-1,4-butanediamine to: 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrole, oxazole, (3,4-tri, spermidine); N-(2-aminoethyl)-1,4-butanediamine isoxazole, thiazole, isothiazole, aZaphosphole, benzopyrro (2,4-tri); N-(6-hexyl)-1,6-hexanediamine (6,6-tri); 1,3,5-tri line, benzopyrrole (indole), benzoxazole, benzisoxazole, aminocyclohexane (tach), 2-(aminomethyl)-1,3-propanedi benzothiazole, benzisothiazole, benzaZaphosphole, diben amine (tamm): 2-(aminomethyl)-2-methyl-1,3-propanedi 45 Zopyrroline, dibenzopyrrole (carbazole), dibenzoxazole, amine (tame): 2-(aminomethyl)-2-ethyl-1,3-propanediamine dibenzisoxazole, dibenzothiazole, dibenzisothiazole, naph (tamp); 1.2.3-triaminopropane (tap); 2.3-(2-aminoethyl) thopyrroline, naphthopyrrole, naphthoxazole, naphthisox aziridine; 2.4-(aminomethyl)aZetidine; 2.5-(aminomethyl) azole, naphthothiazole, naphthisothiazole, naphthaZaphosp pyrrolidine; 2.6-(aminomethyl)piperidine; di(2-aminoben hole, and polypyrroles. Zyl)amine; hexahydro-1,3,5-triazine; hexahydro-2,4,6- 50 NValence Stabilizer #7b. Examples of 5-membered hetero trimethyl-1,3,5-triazine; and 1,3,5-tris(aminomethyl) cyclic rings containing two nitrogen atoms (N monodentates benzene. or N N bidentates) that meet the requirements for use as “wide band' valence stabilizers for Mn" and/or Mn" N Valence Stabilizer #4: Examples of tetramines (N N include, but are not limited to: pyrazoline, imidazoline, imi bidentates, N N tridentates, or N N tetradentates) that 55 dazole (ia), pyrazole, oxadiazole, thiadiazole, diaZaphosp meet the requirements for use as “wide band valence stabi hole, benzopyrazoline, benzimidazoline, benzimidazole lizers for Mn" and/or Mn" include, but are not limited to: (azindole)(bia)(bZ), benzopyrazole (indazole), benzothiadia N,N'-(2-aminoethyl)-1,2-ethanediamine (2.2.2-tet, trien (tri Zole (piazthiole), benzoxadiazole (benzofurazan), naphtho ethylenetetramine)); N,N'-(2-aminoethyl)-1,3-propanedi pyrazoline, naphthimidazoline, naphthimidazole, naphtho amine (2,3,2-tet, entinen); N,N'-(3-aminopropyl)-1,2- 60 ethanediamine (3,2,3-tet, tnentn); N-(2-aminoethyl)-N'-(3- pyrazole, naphthoxadiazole, naphthothiadiazole, aminopropyl)-1,2-ethanediamine (2,2,3-tet); N-(2- polybenzimidazole, and polyimidazoles (e.g. polyvinylimi aminoethyl)-N'-(3-aminopropyl)-1,3-propanediamine dazole (pvi)). (3,3,2-tet); N,N'-(3-aminopropyl)-1,3-propanediamine (3.3, NValence Stabilizer #7c. Examples of 5-membered hetero 3-tet); N,N'-(3-aminopropyl)-1,4-butanediamine (3,4,3-tet, 65 cyclic rings containing three nitrogen atoms (N monoden spermine); tri(aminomethyl)amine (tren); tri(2-aminoethyl) tates, N N bidentates) that meet the requirements for use as amine (trtn); tri(3-aminopropyl)amine (trbn); 2.2-aminom “wide band valence stabilizers for Mn" and/or Mn" US 7,789,958 B2 83 84 include, but are not limited to: triazole, oxatriazole, thiatria and/or Mn' include, but are not limited to: 2-aminoimidazo Zole, benzotriazole (bta), tolyltriazole (tt), naphthotriazole, line: 1-(3-aminopropyl)imidazoline, 2-aminoimidazole; and triazolophthalazine. 1-(3-aminopropyl)imidazole, 4-(2-aminoethyl)imidazole histamine: 1-alkyl-4-(2-aminoethyl)imidazole, 3-(2-ami NValence Stabilizer #7d: Examples of 5-membered hetero noethyl)pyrazole; 3.5-(2-aminoethyl)pyrazole, 1-(aminom cyclic rings containing four nitrogenatoms (N monodentates ethyl)pyrazole; 2-aminobenzimidazole; 7-(2-aminoethyl) or N N bidentates) that meet the requirements for use as benzimidazole: 1-(3-aminopropyl)benzimidazole: 3-(2- “wide band valence stabilizers for Mn" and/or Mn" aminoethyl)indazole; 3.7-(2-aminoethyl)indazole; include, but are not limited to: tetrazole. 1-(aminomethyl)indazole; 7-aminobenzothiadiazole, 4-(2- NValence Stabilizer #8a: Examples of 6-membered hetero 10 aminoethyl)benzothiadiazole; 7-aminobenzoxadiazole; cyclic rings containing one nitrogen atom (N monodentates) 4-(2-aminoethyl)benzoxadiazole; ethylenediaminetetra(1- that meet the requirements for use as “wide band valence pyrazolylmethane) edtp: methylenenitrilotris(2-(1-methyl) stabilizers for Mn" and/or Mn" include, but are not limited benzimidazole) mntbitris(1-methyl-2-benzimidazolyl to: pyridine, picoline, lutidine, y-collidine, oxazine, thiazine, methane)amine; bis(alkyl-1-pyrazolylmethane)amine; bis aZaphosphorin, quinoline, isoquinoline, benzoxazine, ben 15 (alkyl-2-(1-pyrazolyl)ethane)amine; bis(N,N-(2- Zothiazine, benzaZaphosphorin, acridine, phenanthridine, benzimidazolyl)-2-aminoethane)(2- phenothiazine (dibenzothiazine), dibenzoxazine, dibenzaza benzimidazolylmethane)amine; bis(1-(3,5-dimethyl) phosphorin, benzoquinoline (naphthopyridine), naphthoX pyrazolylmethane)phenylamine; tris(2-(1-(3,5-dimethyl) azine, naphthothiazine, naphthaZaphosphorin, and polypy pyrazolyl)ethane)amine; 5-(dimethylamino)pyrazole; ridines. 5-(dimethylaminomethyl)pyrazole; 2-amino-1,3,4-thiadiaz NValence Stabilizer #8b: Examples of 6-membered hetero ole; and 1-(2-aminoethyl)imidazoline. cyclic rings containing two nitrogen atoms (N monodentates or N N bidentates) that meet the requirements for use as NValence Stabilizer #9c. Examples of 5-membered hetero “wide band valence stabilizers for Mn" and/or Mn" 25 cyclic rings containing three nitrogenatoms at least one addi include, but are not limited to: pyrazine, pyridazine, pyrimi tional nitrogen atom binding site not contained in a ring (N dine, oxadiazine, thiadiazine, diaZaphosphorin, quinoxaline Monodentates, N N Bidentates, N N N Tridentates, (benzopyrazine), cinnoline (benzocpyridazine), quinazo N N N N Tetradentates, or N N N N N N line (benzopyrimidine), phthalazine (benzodpyridazine), Hexadentates) that meet the requirements for use as “wide benzoxadiazine, benzothiadiazine, phenazine (dibenzopyra 30 band' valence stabilizers for Mn, and/or Mn" include, but Zine), dibenzopyridazine, naphthopyrazine, naphthopy are not limited to: 3-amino-1,2,4-triazole (ata); 3,5-diamino ridazine, naphthopyrimidine, naphthoxadiazine, naph 1,2,4-triazole (dat); 5-amino-1,2,4-triazole: 3-(2-aminoet thothiadiazine, and polycuinoxalines. hyl)-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; NValence Stabilizer #8c: Examples of 6-membered hetero 35 3.5-(aminomethyl)-4-amino-1,2,4-triazole: 4-(2-aminoet cyclic rings containing three nitrogenatoms (N monodentates hyl)-1,2,3-triazole; 5-(2-aminoethyl)-1,2,3-triazole; 7-ami or N N bidentates) that meet the requirements for use as nobenzotriazole; 1-(aminomethyl)-1,2,3-triazole: 1-(2-ami “wide band' valence stabilizers for Mn" and/or Mn" noethyl)-1,2,3-triazole: 4-(3-aminopropyl)benzotriazole; include, but are not limited to: 1,3,5-triazine, 1,2,3-triazine, benzo-1,2,3-triazine, naphtho-1,2,3-triazine, Oxatriazine, N-(benzotriazolylalkyl)amine: dibenzotriazole-1-ylalky 40 lamine; bis(5-amino-1,2,4-triazol-3-yl); bis(5-amino-1,2,4- thiatriazine, melamine, and cyanuric acid. triazol-3-yl)alkanes; and 1-(aminomethyl)benzotriazole. NValence Stabilizer #8d: Examples of 6-membered hetero cyclic rings containing four nitrogenatoms (N monodentates NValence Stabilizer #9d: Examples of 5-membered hetero or N N bidentates) that meet the requirements for use as cyclic rings containing four nitrogen atoms at least one addi “wide band' valence stabilizers for Mn" and/or Mn" 45 tional nitrogen atom binding site not contained in a ring (N Monodentates, N N Bidentates, N N Tridentates, N N include, but are not limited to: tetrazine. Tetradentates, or N N Hexadentates) that meet the require NValence Stabilizer #9a: Examples of 5-membered hetero ments for use as “wide band” valence stabilizers for Mn' cyclic rings containing one nitrogenatom and having at least and/or Mn' include, but are not limited to:5-(2-aminoethyl)- one additional nitrogen atom binding site not contained in a 1H-tetrazole: 1-(aminomethyl)-1H-tetrazole; and 1-(2-ami ring (NMonodentates, N N Bidentates, N N Tridentates, 50 noethyl)-1H-tetrazole. N N Tetradentates, or N N Hexadentates) that meet the requirements for use as “wide band valence stabilizers for NValence Stabilizer #10a: Examples of 6-membered hetero Mn" and/or Mn" include, but are not limited to: 2-(aminom cyclic rings containing one nitrogenatom and having at least ethyl)-3-pyrroline; 2.5-(aminomethyl)-3-pyrroline: 2-(ami one additional nitrogen atom binding site not contained in a nomethyl)pyrrole; 2.5-(aminomethyl)pyrrole, 3-(aminom 55 ring (NMonodentates, N N Bidentates, N N Tridentates, ethyl)isoxazole: 2-(aminomethyl)thiazole; 3-(aminomethyl) N N Tetradentates, or N N Hexadentates) that meet the isothiazole, 2-(aminomethyl)indole: 2-aminobenzoxazole; requirements for use as “wide band valence stabilizers for 2-aminobenzothiazole (abt); 1,8-diaminocarbazole; Mn" and/or Mn' include, but are not limited to: 2-aminopy 2-amino-6-methyl-benzothiazole (amebt); 2-amino-6-meth ridine; 2,6-diaminopyridine: 2-(aminomethyl)pyridine; 2.6- 60 (aminomethyl)pyridine; 2,6-(aminoethyl)pyridine, 2-amino oxybenzothiazole (ameobt), and 1,3-diiminoisoindoline. 4-picoline; 2,6-diamino-4-picoline, 2-amino-3.5-lutidine; NValence Stabilizer #9b: Examples of 5-membered hetero 2-aminoquinoline; 8-aminoquinoline: 2-aminoisoquinoline; cyclic rings containing two nitrogen atoms at least one addi acriflavine, 4-aminophenanthridine, 4.5-(aminomethyl)phe tional nitrogen atom binding site not contained in a ring (N nothiazine; 4.5-(aminomethyl)dibenzoxazine; 10-amino-7, Monodentates, N N Bidentates, N N Tridentates, N N 65 8-benzoquinoline; bis(2-pyridylmethane)amine; tris(2-py Tetradentates, or N N Hexadentates) that meet the require ridyl)amine; bis(4-(2-pyridyl)-3-azabutane)amine; bis(N.N- ments for use as “wide band” valence stabilizers for Mn' (2-(2-pyridyl)ethane)aminomethane)amine; 4-(N.N- US 7,789,958 B2 85 86 dialkylaminomethyl)morpholine; 6-aminonicotinic acid; thiazolyl)benzimidazole: 2-(2-imidazolyl)benzimidazole; 8-aminoacridine; and 2-hydrazinopyridine. benzimidazotriazine, 4-aZabenzimidazole; and 2,6-bis(2- benzimidazolyl)pyridine. NValence Stabilizer #10b. Examples of 6-membered hetero cyclic rings containing two nitrogen atoms at least one addi 5 NValence Stabilizer #11c. Examples of 5-membered hetero tional nitrogen atom binding site not contained in a ring (N cyclic rings containing three nitrogenatoms at least one addi Monodentates, N N Bidentates, N N Tridentates, N N tional nitrogen atom binding site contained in a ring (N Tetradentates, or N N Hexadentates) that meet the require Monodentates, N N Bidentates, N N Tridentates, N N ments for use as “wide band valence stabilizers for Mn" Tetradentates) that meet the requirements for use as “wide and/or Mn" include, but are not limited to: 2-aminopyrazine; 10 band valence stabilizers for Mn" and/or Mn" include, but 2,6-diaminopyrazine: 2-(aminomethyl)pyrazine; 2.6-(ami are not limited to: 5,5'-bi-1,2,4-triazolebtrz; 3,3'-bi-1,2,4- nomethyl)pyrazine; 3-(aminomethyl)pyridazine; 3.6-(ami triazole; 1,1'-bi-1,2,4-triazole; 1,1'-bi-1,2,3-triazole; 5,5'-bi nomethyl)pyridazine; 3.6-(2-aminoethyl)pyridazine: 1-ami 1,2,3-triazole; 7.7'-bibenzotriazole; 1,1'-bibenzotriazole; bis nopyridazine; 1-(aminomethyl)pyridazine; (pyridyl)aminotriazole (pat); and 8-azaadenine. 2-aminopyrimidine: 1-(2-aminoethyl)pyrimidine, 2-amino 15 quinoxaline: 2,3-diaminoquinoxaline: 2-aminocinnoline; NValence Stabilizer #11d. Examples of 5-membered hetero 3-aminocinnoline; 3-(2-aminoethyl)cinnoline; 3.8-(2-ami cyclic rings containing four nitrogen atoms at least one addi noethyl)cinnoline; 2-aminoquinazoline: 1-(2-aminoethyl) tional nitrogen atom binding site contained in a ring (N quinazoline: 1-aminophthalazine, 1,4-(2-aminoethyl)ph Monodentates, N N Bidentates, N N Tridentates, N N thalazine; 1.8-(aminomethyl)phenazine, 2-amino-4,6- Tetradentates) that meet the requirements for use as “wide dimethylpyrimidine (admp); dihydralazine; and hydralazine. band' valence stabilizers for Mn, and/or Mn" include, but NValence Stabilizer #10c: Examples of 6-membered hetero are not limited to: 5,5'-bi-1H-tetrazole; and 1,1'-bi-1H-tetra cyclic rings containing three nitrogenatoms at least one addi Zole. tional nitrogen atom binding site not contained in a ring (N NValence Stabilizer #12a: Examples of 6-membered hetero Monodentates, N N Bidentates, N N Tridentates, N N 25 cyclic rings containing one nitrogenatom and having at least Tetradentates, or N N Hexadentates) that meet the require one additional nitrogen atom binding site contained in a ring ments for use as “wide band” valence stabilizers for Mn' (N Monodentates, N N Bidentates, N N Tridentates, and/or Mn" include, but are not limited to: 2-amino-1,3,5- N N Tetradentates) that meet the requirements for use as triazine, 2-(aminomethyl)-1,3,5-triazine; 2,6-(aminom 30 “wide band' valence stabilizers for Mn" and/or Mn" ethyl)-1,3,5-triazine: 1-(3-aminopropyl)-1,3,5-triazine; 1.5- include, but are not limited to: 2,2'-bipyridine bipy; 2.2.2"- (3-aminopropyl)-1,3,5-triazine, polymelamines; melamine; tripyridine terpyridine terpy; 2.2.2".2"-tetrapyridine tet and altretamine. rapy; 6,6'-bi-2-picoline; 6,6'-bi-3-picoline; 6,6'-bi-4-pi NValence Stabilizer #10d: Examples of 6-membered hetero coline; 6,6'-bi-2,3-lutidine; 6,6'-bi-2,4-lutidine; 6,6'-bi-3,4- cyclic rings containing four nitrogen atoms at least one addi 35 lutidine; 6,6'-bi-2,3,4-collidine: 2,2'-biquinoline: 2,2'- tional nitrogen atom binding site not contained in a ring (N bisoquinoline; 3,3'-bibenzoxazine; 3,3'-bibenzothiazine; Monodentates, N N Bidentates, N N Tridentates, N N 1,10-phenanthroline phen; 1,8-naphthyridine; bis-1,2-(6- Tetradentates, or N N Hexadentates) that meet the require (2,2'-bipyridyl)ethane; bis-1,3-(6-(2,2'-bipyridyl))propane: ments for use as “wide band” valence stabilizers for Mn' 3,5-bis(3-pyridyl)pyrazole; 3,5-bis(2-pyridyl)triazole; 1,3- and/or Mn" include, but are not limited to. 3,6-(2-aminoet 40 bis(2-pyridyl)-1,3,5-triazine; 1,3-bis(2-pyridyl)-5-(3-py hyl)-1,2,4,5-tetrazine; 3.6-(1,3-diamino-2-propyl)-1,2,4,5- ridyl)-1,3,5-triazine; 2.7-(N,N'-di-2-pyridyl)diaminoben tetrazine; and 4.6-(aminomethyl)-1,2,3,5-tetrazine. Zopyrroline; 2.7-(N,N'-di-2-pyridyl)diaminophthalazine: NValence Stabilizer #11a: Examples of 5-membered hetero 2,6-di-(2-benzothiazolyl)pyridine; triazolopyrimidine: 2-(2- cyclic rings containing one nitrogenatom and having at least pyridyl)imidazoline; 7-azaindole: 1-(2-pyridyl)pyrazole; one additional nitrogen atom binding site contained in a ring 45 (1-imidazolyl)(2-pyridyl)methane; 4,5-bis(N,N'-(2-(2-py (N Monodentates, N N Bidentates, N N Tridentates, ridyl)ethyl)iminomethyl)imidazole; bathophenanthroline; N N Tetradentates) that meet the requirements for use as 4-(2-benzimidazolyl)cquinoline; 1,2-bis(2-pyridyl)ethane; “wide band valence stabilizers for Mn" and/or Mn" 4,4'-diphenyl-2,2'-dipyridyll; neocuproine; nicotine; and nor include, but are not limited to: 2,2'-bi-3-pyrroline: 2,2'-bi-2- nicotine. pyrroline: 2,2'-bi-1-pyrroline: 2,2'-bipyrrole; 2.2.2"-tripyr 50 NValence Stabilizer #12b: Examples of 6-membered hetero role; 3,3'-bisoxazole; 2,2'-bioxazole; 3,3'-bisothiazole; 2,2'- cyclic rings containing two nitrogen atoms at least one addi bithiazole; 2,2'-bindole; 2,2'-bibenzoxazole; 2,2'- tional nitrogen atom binding site contained in a ring (N bibenzothiazole; bilirubin; biliverdine; and 7-azaindole. Monodentates, N N Bidentates, N N Tridentates, N N NValence Stabilizer #11b: Examples of 5-membered hetero 55 Tetradentates) that meet the requirements for use as “wide cyclic rings containing two nitrogen atoms at least one addi band' valence stabilizers for Mn, and/or Mn" include, but tional nitrogen atom binding site contained in a ring (N are not limited to: 2,2'-bipyrazine; 2.2.2"-tripyrazine; 6,6'- Monodentates, N N Bidentates, N N Tridentates, N N bipyridazine; bis(3-pyridazinyl)methane; 1.2-bis(3-pyridazi Tetradentates) that meet the requirements for use as “wide nyl)ethane: 2,2'-bipyrimidine: 2,2'-biquinoxaline; 8.8-biqui band valence stabilizers for Mn" and/or Mn" include, but 60 noxaline; bis(3-cinnolinyl)methane; bis(3-cinnolinyl)ethane: are not limited to: 2,2'-bi-2-imidazoline2,2'-bi-2-imidazoli 8.8'-bicinnoline: 2,2'-biquinazoline; 4,4'-biquinazoline; 8.8- nylbimd: 2,2'-biimidazole2,2'-biimidazolylbiimH: biquinazoline: 2,2'-biphthalazine; 1,1'-biphthalazine: 2-(2- 5,5'-bipyrazole; 3,3'-bipyrazole; 4,4'-bipyrazole4,4'-bipyra pyridyl)benzimidazole; 8-azapurine; purine; adenine; gua Zolylbpz: 2,2'-bioxadiazole; 2,2'-bithiadiazole; 2,2'-biben nine; hypoxanthine; 2,6-bis(N,N'-(2-(4-imidazolyl)ethyl) Zimidazole; 7.7-bindazole; 5,5'-bibenzofurazan: 5,5'-biben 65 iminomethyl)pyridine; 2-(N-(2-(4-imidazolyl)ethyl) Zothiadiazole; bis-1,2-(2-benzimidazole)ethane; bis(2- iminomethyl)pyridine; adenine (aminopurine); purine; and benzimidazole)methane; 1.2-(2-imidazolyl)benzene: 2-(2- 2,3-bis(2-pyridyl)pyrazine. US 7,789,958 B2 87 88 NValence Stabilizer #12c: Examples of 6-membered hetero clooctane (8aneN); tetraazacyclononane (9aneN); tet cyclic rings containing three nitrogenatoms at least one addi raazacyclodecane (10aneN); tetraazacycloundecane (11 tional nitrogen atom binding site contained in a ring (N aneN); tetraazacyclododecane (12aneN); Monodentates, N N Bidentates, N N Tridentates, N N tetraazacyclotridecane (13aneN); tetraazacyclotetrade Tetradentates) that meet the requirements for use as “wide cane (14aneN); tetraazacyclopentadecane (15aneN); band valence stabilizers for Mn" and/or Mn" include, but tetraazacyclohexadecane (16aneN); tetraazacyclohepta are not limited to: 2,2'-bi-1,3,5-triazine; 2,2', 2'-tri-1,3,5- decane (17aneN); tetraazacyclooctadecane (18aneN); triazine; 4,4'-bi-1,2,3-triazine; and 4,4'-bibenzo-1,2,3-triaz tetraazacyclononadecane (19aneN), tetraazacycloe ine; 2,4,6-tris(2-pyridyl)-1,3,5-triazine; and benzimidazotri icosane (20aneN); tetraazacyclooctadiene (8dieneN); azines. 10 tetraazacyclononadiene (9dieneN); tetraazacyclodecadi NValence Stabilizer #12d: Examples of 6-membered hetero ene (1 OdieneN); tetraazacycloundecadiene (11dieneN); cyclic rings containing four nitrogen atoms at least one addi tetraazacyclododecadiene (12dieneN); tetraazacyclot tional nitrogen atom binding site contained in a ring (N ridecadiene (13dieneN); tetraazacyclotetradecadiene (14 Monodentates, N N Bidentates, N N Tridentates, N N dieneN), tetraazacyclopentadecadiene (15dieneN); tet 15 raazacyclohexadecadiene (16dieneN); Tetradentates) that meet the requirements for use as “wide tetraazacycloheptadecadiene (17dieneN); tetraazacy band' valence stabilizers for Mn" and/or Mn" include, but clooctadecadiene (18dieneN); tetraazacyclononadecadi are not limited to: 3,3'-bi-1,2,4,5-tetrazine; and 4,4'-bi-1,2,3, ene (19dieneN); tetraazacycloeicosadiene (I2OdieneN); 5-tetrazine. tetraazacyclooctatetradiene (8tetradieneN); tetraazacy NValence Stabilizer #13a: Examples of two-membered mac clononatetradiene (9tetradieneN); tetraazacyclodecatetra rocyclics, macrobicyclics, and macropolycyclics (including diene (10 tetradieneN); tetraazacycloundecatetradiene catapinands, cryptands, cyclidenes, and sepulchrates) (11tetradieneN); tetraazacyclododecatetradiene (12tet wherein both binding sites are composed of nitrogen (usually radieneN); tetraazacyclotridecatetradiene (13 tetradi amine or imine groups) and are not contained in component eneN); tetraazacyclotetradecatetradiene (14tetradieneN); heterocyclic rings (N N Bidentates) that meet the require 25 tetraazacyclopentadecatetradiene (15tetradieneN); tet ments for use as “wide band valence stabilizers for Mn" raazacyclohexadecatetradiene (16 tetradieneN); tetraaza and/or Mn' include, but are not limited to: diazacyclobutane cycloheptadecatetradiene (17tetradieneN); tetraazacy (4 laneN); diazacyclopentane (5aneN); diazacyclohex clooctadecatetradiene (18tetradieneN); ane (6aneN); diazacycloheptane (7aneN); diazacy tetraazacyclononadecatetradiene (19tetradieneN); and tet clooctane (8 laneN); piperazine; benzopiperazine; diazacy 30 raazacycloeicosatetradiene (20 tetradieneN). clobutene (4eneN); diazacyclopentene (5eneN); NValence Stabilizer #13d: Examples of six-membered mac diazacyclohexene (6eneN); diazacycloheptene (7 rocyclics, macrobicyclics, and macropolycyclics (including eneN); diazacyclooctene (8 eneN); diazacyclobutadiene catapinands, cryptands, cyclidenes, and sepulchrates) (4dieneN); diazacyclopentadiene (5dieneN); diazacy wherein all binding sites are composed of nitrogen (usually clohexadiene (6dieneN); diazacycloheptadiene (7di 35 amine or imine groups) and are not contained in component eneN); and diazacyclooctadiene (8dieneN) heterocyclic rings (N N Tridentates, N N Tetradentates, N Valence Stabilizer #13b. Examples of three-membered or N N Hexadentates) that meet the requirements for use as macrocyclics, macrobicyclics, and macropolycyclics (in “wide band valence stabilizers for Mn" and/or Mn" cluding catapinands, cryptands, cyclidenes, and sepulch include, but are not limited to: hexaazacyclododecane (12 rates) wherein all binding sites are composed of nitrogen 40 aneN); hexaazacyclotridecane (13aneN); hexaazacy (usually amine or imine groups) and are not contained in clotetradecane (14aneN); hexaazacyclopentadecane (15 component heterocyclic rings (N N Tridentates) that meet aneN); hexaazacyclohexadecane (16aneN); the requirements for use as “wide band valence stabilizers hexaazacycloheptadecane (17aneN); hexaazacyclooctade for Mn" and/or Mn" include, but are not limited to: triaza cane (18 aneN); hexaazacyclononadecane (19aneN); cyclohexane (including hexahydro-1,3,5-triazine)(6) 45 hexaazacycloeicosane (20aneN), hexaazacyclohene aneN); triazacycloheptane (7aneN); triazacyclooctane icosane (21 laneN); hexaazacyclodocosane (22aneN); (8 laneN); triazacyclononane (9aneN), triazacyclode hexaazacyclotricosane (23aneN); hexaazacyclotetra cane (10aneN), triazacycloundecane (11 laneN); triaza cosane (24aneN), hexaazacyclododecatriene (12 cyclododecane (12aneN), triazacyclohexene (6eneN); trieneN); hexaazacyclotridecatriene (13trieneN); triazacycloheptene (7eneN); triazacyclooctene (8 50 hexaazacyclotetradecatriene (14trieneN); hexaazacyclo eneN); triazacyclononene (9eneN); triazacyclodecene pentadecatriene (15 trieneN); hexaazacyclohexadecatriene (10eneN), triazacycloundecene (11eneN); triazacy (16trieneN); hexaazacycloheptadecatriene (17trieneN); clododecene (12eneN); triazacyclohexatriene (I6 hexaazacyclooctadecatriene (18trieneN); hexaazacy trieneN); triazacycloheptatriene (7trieneN); triazacy clononadecatriene (19trieneN); hexaazacycloeicosatriene clooctatriene (8trieneN); triazacyclononatriene (9) 55 (20 trieneN); hexaazacycloheneicosatriene (21 trieneN); trieneN); triazacyclodecatriene (10 trieneN); hexaazacyclodocosatriene (22trieneN); hexaazacyclotri triazacycloundecatriene (11trieneN); and triazacy cosatriene (23 trieneN); and hexaazacyclotetracosatriene clododecatriene (12trieneN). (24trieneN). NValence Stabilizeril 13c. Examples of four-membered mac 60 N Valence Stabilizer #13e: Examples of eight-membered rocyclics, macrobicyclics, and macropolycyclics (including macrocyclics, macrobicyclics, and macropolycyclics (in catapinands, cryptands, cyclidenes, and sepulchrates) cluding catapinands, cryptands, cyclidenes, and sepulch wherein all binding sites are composed of nitrogen (usually rates) wherein all binding sites are composed of nitrogen amine or imine groups) and are not contained in component (usually amine or imine groups) and are not contained in heterocyclic rings (N N Tetradentates) that meet the 65 component heterocyclic rings (N NTridentates, N N Tet requirements for use as “wide band valence stabilizers for radentates, or N N Hexadentates) that meet the require Mn" and/or Mn" include, but are not limited to: tetraazacy ments for use as “wide band” valence stabilizers for Mn' US 7,789,958 B2 89 90 and/or Mn' include, but are not limited to: octaazacyclo tetratriazoles; tetraoxatriazoles; tetrathiatriazoles; copropor hexadecane (16aneNs); octaazacycloheptadecane (17 phyrin, etioporphyrin, and hematoporphyrin. aneNs); octaazacyclooctadecane (18 laneNs); octaazacy clononadecane (19aneNs); octaazacycloeicosane (20 NValence Stabilizer #14b: Examples of six-membered mac aneNs); octaazacycloheneicosane (21 aneNs); rocyclics, macrobicyclics, and macropolycyclics (including octaazacyclodocosane (22aneNs); octaazacyclotricosane catapinands, cryptands, cyclidenes, and sepulchrates) (23aneNs); octaazacyclotetracosane (24 laneNs); octaaza wherein all six binding sites are composed of nitrogen and are cyclohexadecatetradiene (16 tetradieneNs); octaazacyclo contained in component 5-membered heterocyclic rings heptadecatetradiene (17tetradieneNs); octaazacyclooctade (N N Tridentates, N N Tetradentates, or N N Hexaden 10 tates) that meet the requirements for use as “wide band catetradiene (18tetradieneNs); valence stabilizers for Mn" and/or Mn" include, but are not octaazacyclononadecatetradiene (19tetradieneNs); limited to: hexaphyrins (hexapyrroles); hexaoxazoles; hexai octaazacycloeicosatetradiene (20tetradieneNs); octaazacy Sooxazoles; hexathiazoles; hexaisothiazoles; hexaazaphosp cloheneicosatetradiene (21 tetradieneNs); octaazacy holes; hexaimidazoles; hexapyrazoles; hexaoxadiazoles; clodocosatetradiene (22 tetradieneNs); octaazacyclotrico 15 satetradiene (23tetradieneNs); and hexathiadiazoles; hexadiaZaphospholes; hexatriazoles; octaazacyclotetracosatetradiene (24tetradieneNs). hexaoxatriazoles; and hexathiatriazoles. NValence Stabilizer #13f. Examples often-membered mac N Valence Stabilizer #14c. Examples of eight-membered rocyclics, macrobicyclics, and macropolycyclics (including macrocyclics, macrobicyclics, and macropolycyclics (in catapinands, cryptands, cyclidenes, and sepulchrates) cluding catapinands, cryptands, cyclidenes, and sepulch wherein all binding sites are composed of nitrogen (usually rates) wherein all eight binding sites are composed of nitro amine or imine groups) and are not contained in component gen and are contained in component 5-membered heterocyclic rings (N N Tridentates, N N Tetradentates, heterocyclic rings (N N Tridentates, N N Tetradentates, or N N Hexadentates) that meet the requirements for use as or N N Hexadentates) that meet the requirements for use as “wide band' valence stabilizers for Mn" and/or Mn" 25 “wide band valence stabilizers for Mn" and/or Mn" include, but are not limited to: decaazacycloeicosane (20 include, but are not limited to: octaphyrins (octapyrroles); aneNo); decaazacycloheneicosane (21 laneNo); decaaza octaoxazoles; octaisooxazoles; octathiazoles; octaisothiaz cyclodocosane (22aneNo); decaazacyclotricosane (23 oles; octaaZaphospholes; octaimidazoles; octapyrazoles; aneNo); decaazacyclotetracosane (24laneNo); octaoxadiazoles; octathiadiazoles; octadiaZaphospholes; decaazacyclopentacosane (25aneNo); decaazacyclohexa 30 octatriazoles; octaoxatriazoles; and octathiatriazoles. cosane (26aneNo); decaazacycloheptacosane (27 NValence Stabilizer #14d. Examples often-membered mac aneNo); decaazacyclooctacosane (28aneNo); decaazacy rocyclics, macrobicyclics, and macropolycyclics (including clononacosane (29aneNo); decaazacyclotriacontane (30 aneNo); decaazacycloeicosapentadiene (20 catapinands, cryptands, cyclidenes, and sepulchrates) pentadieneNo); decaazacycloheneicosapentadiene (21 35 wherein all ten binding sites are composed of nitrogen and are pentadieneNo); decaazacyclodocosapentadiene (22 contained in component 5-membered heterocyclic rings pentadieneNo); decaazacyclotricosapentadiene (23 (N N Tridentates, N N Tetradentates, or N N Hexaden pentadieneNo); decaazacyclotetracosapentadiene (24 tates) that meet the requirements for use as “wide band pentadieneNo); decaazacyclopentacosapentadiene (25 valence stabilizers for Mn" and/or Mn' include, but are not pentadieneNo); decaazacyclohexacosapentadiene (26 40 limited to: decaphyrins (decapyrroles); decaoxazoles; decai pentadieneNo); decaazacycloheptacosapentadiene (27 Sooxazoles; decathiazoles; decaisothiazoles; decaaZaphosp pentadieneNo); decaazacyclooctacosapentadiene (28 holes; decaimidazoles; decapyrazoles; decaoxadiazoles; pentadieneNo); decaazacyclononacosapentadiene (29 decathiadiazoles; decadiaZaphospholes; decatriazoles; deca pentadieneNo); and decaazacyclotriacontapentadiene (30 oXatriazoles; and decathiatriazoles. pentadieneNo). 45 NValence Stabilizer #15a: Examples of four-membered mac NValence Stabilizer #14a: Examples of four-membered mac rocyclics, macrobicyclics, and macropolycyclics (including rocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and wherein all four binding sites are composed of nitrogen and 50 are contained in a combination of 5-membered heterocyclic are contained in component 5-membered heterocyclic rings rings and amine or imine groups (N N Tetradentates) that (N N Tetradentates) that meet the requirements for use as meet the requirements for use as “wide band valence stabi “wide band valence stabilizers for Mn" and/or Mn" lizers for Mn" and/or Mn" include, but are not limited to: include, but are not limited to: porphyrins (including tet porphyrazines; octahydrodiazaporphyrins; phthalocyanines; raphenylporphine (tpp); "picket fence' porphyrins, "picket 55 tail porphyrins, “bispocket' porphyrins, “capped porphy naphthalocyanines; anthracocyanines; and tetraazaporphy rins, cyclophane porphyrins, 'pagoda' porphyrins, "pocket' rins porphyrins, “pocket tail porphyrins, cofacial diporphyrins, NValence Stabilizer #15b: Examples of six-membered mac “strapped’ porphyrins, "hanging base' porphyrins, bridged rocyclics, macrobicyclics, and macropolycyclics (including porphyrins, chelated mesoporphyrins, homoporphyrins, 60 catapinands, cryptands, cyclidenes, and sepulchrates) chlorophylls, and pheophytins); porphodimethanes; porphy wherein all six binding sites are composed of nitrogen and are rinogens; chlorins; bacteriochlorins; isobacteriochlorins; contained in a combination of 5-membered heterocyclic rings corroles; corrins and corrinoids; didehydrocorrins; tetradehy and amine or imine groups (N N Tridentates, N N Tet drocorrins; hexadehydrocorrins; octadehydrocorrins; tet radentates, or N N Hexadentates) that meet the require raoxazoles; tetraisooxazoles; tetrathiazoles; tetraisothiaz 65 ments for use as “wide band” valence stabilizers for Mn' oles; tetraaZaphospholes; tetraimidazoles; tetrapyrazoles; and/or Mn" include, but are not limited to: diazahexaphy tetraoxadiazoles; tetrathiadiazoles; tetradiaZaphospholes; rins; tetraaZahexaphyrins; hexaazahexaphyrins; diaza US 7,789,958 B2 91 92 hexapyrazoles; tetraazahexapyrazoles; hexaazahexapyra and are contained in component 6-membered heterocyclic Zoles; diazahexaimidazoles; tetraaZahexaimidazoles; and rings (N N Tridentates, N N Tetradentates, or N N hexaazahexaimidazoles. Hexadentates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but N Valence Stabilizer #15c. Examples of eight-membered are not limited to: cyclooctapyridines; cyclooctaoxazines; macrocyclics, macrobicyclics, and macropolycyclics (in cyclooctathiazines; cyclooctaphosphorins; cyclooctaquino cluding catapinands, cryptands, cyclidenes, and sepulch lines; cyclooctapyrazines; cyclooctapyridazines; cyclooc rates) wherein all eight binding sites are composed of nitro tapyrimidines; cyclooctaoxadiazines; cyclooctathiadiazines; gen and are contained in a combination of 5-membered cyclooctadiaZaphosphorins; cyclooctaquinoxalines; heterocyclic rings and amine orimine groups (N N Triden 10 cyclooctatriazines; cyclooctathiatriazines; and cyclooctaox tates, N N Tetradentates, or N N Hexadentates) that meet atriazines. the requirements for use as “wide band valence stabilizers NValence Stabilizer #16d: Examples often-membered mac for Mn' and/or Mn" include, but are not limited to: diaza rocyclics, macrobicyclics, and macropolycyclics (including octaphyrins; tetraazaoctaphyrins; hexaazaoctaphyrins; catapinands, cryptands, cyclidenes, and sepulchrates) octaaZaoctaphyrins; diazaoctapyrazoles; tetraaZaoctapyra 15 wherein all six binding sites are composed of nitrogen and are Zoles; hexaazaoctapyrazoles; octaaZaoctapyrazoles; diazaoc contained in component 6-membered heterocyclic rings taimidazoles; tetraaZaoctaimidazoles; hexaazaoctaimida (N N Tridentates, N N Tetradentates, or N N Hexaden Zoles; and octaaZaoctaimidazoles. tates) that meet the requirements for use as “wide band NValence Stabilizer #15d: Examples often-membered mac valence stabilizers for Mn" and/or Mn' include, but are not rocyclics, macrobicyclics, and macropolycyclics (including limited to: cyclodecapyridines; cyclodecaoxazines; cyclode catapinands, cryptands, cyclidenes, and sepulchrates) cathiazines; cyclodecaphosphorins; cyclodecaduinolines; wherein all ten binding sites are composed of nitrogen and are cyclodecapyrazines; cyclodecapyridazines; cyclodecapyrim contained in a combination of 5-membered heterocyclic rings idines; cyclodecaoxadiazines; cyclodecathiadiazines; cyclo and amine or imine groups (N N Tridentates, N N Tet decadiaZaphosphorins; cyclodecaduinoxalines; cyclodecatri radentates, or N N Hexadentates) that meet the require 25 azines; cyclodecathiatriazines; and cyclodecaoxatriazines. ments for use as “wide band” valence stabilizers for Mn' and/or Mn' include, but are not limited to: diazadecaphyrins; NValence Stabilizeril 17a: Examples of four-membered mac tetraazadecaphyrins; hexaazadecaphyrins; octaaZadecaphy rocyclics, macrobicyclics, and macropolycyclics (including rins; decaaZadecaphyrins; diazadecapyrazoles; tetraazade catapinands, cryptands, cyclidenes, and sepulchrates) capyrazoles; hexaazadecapyrazoles; octaaZadecapyrazoles; 30 wherein all four binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic decaazadecapyrazoles; diazadecaimidazoles; tetraaza rings and amine or imine groups (N N Tetradentates) that decaimidazoles; hexaazadecaimidazoles; octaaZadecaimida meet the requirements for use as “wide band valence stabi Zoles; and decaaZadecaimidazoles. lizers for Mn" and/or Mn" include, but are not limited to: NValence Stabilizeril 16a: Examples of four-membered mac 35 diazacyclotetrapyridines; tetraazacyclotetrapyridines; diaza rocyclics, macrobicyclics, and macropolycyclics (including cyclotetracquinolines; tetraazacyclotetracquinolines; diazacy catapinands, cryptands, cyclidenes, and sepulchrates) clotetrapyrazines; tetraazacyclotetrapyrazines; diazacy wherein all four binding sites are composed of nitrogen and clotetrapyridazines; tetraazacyclotetrapyridazines; are contained in component 6-membered heterocyclic rings diazacyclotetrapyrimidines; tetraazacyclotetrapyrimidines; (N N Tetradentates) that meet the requirements for use as 40 diazacyclotetratriazines; and tetraazacyclotetratriazines. “wide band valence stabilizers for Mn" and/or Mn" NValence Stabilizer #17b: Examples of six-membered mac include, but are not limited to: cyclotetrapyridines; cyclotet rocyclics, macrobicyclics, and macropolycyclics (including raoxazines; cyclotetrathiazines; cyclotetraphosphorins; catapinands, cryptands, cyclidenes, and sepulchrates) cyclotetracquinolines; cyclotetrapyrazines; cyclotetrapy wherein all six binding sites are composed of nitrogen and are ridazines; cyclotetrapyrimidines; cyclotetraoxadiazines; 45 cyclotetrathiadiazines; cyclotetradiaZaphosphorins; cyclotet contained in a combination of 6-membered heterocyclic rings raquinoxalines; cyclotetratriazines; cyclotetrathiatriazines; and amine or imine groups (N N Tridentates, N N Tet radentates, or N N Hexadentates) that meet the require and cyclotetraoxatriazines. ments for use as “wide band” valence stabilizers for Mn' NValence Stabilizer #16b: Examples of six-membered mac and/or Mn" include, but are not limited to: diazacyclosex rocyclics, macrobicyclics, and macropolycyclics (including 50 ipyridines; triazacycloSexipyridines; diazacyclosexiquino catapinands, cryptands, cyclidenes, and sepulchrates) lines; triazacyclosexiquinolines; diazacyclosexipyrazines; wherein all six binding sites are composed of nitrogen and are triazacycloSexipyrazines; diazacycloSexipyridazines; triaza contained in component 6-membered heterocyclic rings cycloSexipyridazines; diazacycloSexipyrimidines; triazacy (N N Tridentates, N N Tetradentates, or N N Hexaden closexipyrimidines; diazacyclosexitriazines; and triazacyclo tates) that meet the requirements for use as “wide band 55 sexitriazines. valence stabilizers for Mn" and/or Mn" include, but are not limited to: cyclosexipyridines; cyclosexioxazines; cyclo N Valence Stabilizer #17c. Examples of eight-membered sexithiazines; cycloSexiphosphorins; cyclosexiquinolines; macrocyclics, macrobicyclics, and macropolycyclics (in cyclosexipyrazines; cycloSexipyridazines; cyclosexipyrim cluding catapinands, cryptands, cyclidenes, and sepulch idines; cyclosexioxadiazines; cyclosexithiadiazines; cyclo 60 rates) wherein all eight binding sites are composed of nitro sexidiaZaphosphorins cyclosexicuinoxalines; cyclosexitriaz gen and are contained in a combination of 6-membered ines; cyclosexithiatriazines; and cyclosexioXatriazines. heterocyclic rings and amine orimine groups (N N Triden tates, N N Tetradentates, or N N Hexadentates) that meet N Valence Stabilizer #16c. Examples of eight-membered the requirements for use as “wide band valence stabilizers macrocyclics, macrobicyclics, and macropolycyclics (in 65 for Mn' and/or Mn" include, but are not limited to: diaza cluding catapinands, cryptands, cyclidenes, and sepulch cyclooctapyridines; tetraazacyclooctapyridines; diazacy rates) wherein all six binding sites are composed of nitrogen clooctaquinolines; tetraazacyclooctaquinolines; diazacy US 7,789,958 B2 93 94 clooctapyrazines; tetraazacyclooctapyrazines; dinaphthylbiguanide; dicyclohexylbiguanide; dinorbornyl diazacyclooctapyridazines; tetraazacyclooctapyridazines; biguanide; diadamantylbiguanide; ethylenedibiguanide; pro diazacyclooctapyrimidines; tetraazacyclooctapyrimidines; pylenedibiguanide; tetramethylenedibiguanide; pentameth diazacyclooctatriazines; and tetraazacyclooctatriazines. ylenedibiguanide; hexamethylenedibiguanide; heptamethylenedibiguanide; octamethylenedibiguanide; NValence Stabilizer #17d: Examples often-membered mac phenylenedibiguanide; piperazinedibiguanide; oxalyldibigu rocyclics, macrobicyclics, and macropolycyclics (including anide; malonyldilbiguanide. Succinyldilbiguanide; glu catapinands, cryptands, cyclidenes, and sepulchrates) taryldilbiguanide; adipyldibiguanide; pimelyldibiguanide; wherein all ten binding sites are composed of nitrogen and are Suberyldibiguanide; phthalyldibiguanide; paludrine; poly contained in a combination of 6-membered heterocyclic rings 10 hexamethylene biguanide; 2-guanidinothiazole; 2-guanidi and amine or imine groups (N N Tridentates, N N Tet nooxazole; 2-guanidinoimidazole, 3-guanidinopyrazole; radentates, or N N Hexadentates) that meet the require ments for use as “wide band” valence stabilizers for Mn' 3-guanidino-1,2,4-triazole; 5-guanidinotetrazole; alexidine; and/or Mn" include, but are not limited to: diazacyclode buformin; and moroxydine. capyridines; pentaazacyclodecapyridines; diazacyclode 15 NValence Stabilizer #20: Examples of diamidinomethanes, caquinolines; pentaazacyclodecaduinolines; diazacyclode bis(diamidinomethanes), and poly(diamidinomethanes) capyrazines; pentaazacyclodecapyrazines; (N N bidentates, N N tridentates, N N tetradentates, diazacyclodecapyridazines; pentaazacyclodecapyridazines; and N N hexadentates) that meet the requirements for use as diazacyclodecapyrimidines; pentaazacyclodecapyrimidines; “wide band' valence stabilizers for Mn" and/or Mn" diazacyclodecatriazines; and pentaazacyclodecatriazines. include, but are not limited to: diamidinomethane; N-meth yldiamidinomethane; N-ethyldiamidinomethane; N-isopro N Valence Stabilizer #18: Examples of amidines and dia pyldiamidinomethane; N-butyldiamidinomethane; N-ben midines (N N bidentates or N N Tetradentates) that meet Zyldiamidinomethane; N-phenyldiamidinomethane: the requirements for use as “wide band valence stabilizers for Mn" and/or Mn include, but are not limited to: N,N'- N-tolyldiamidinomethane; N-naphthyldiamidinomethane: dimethylformamidine; N.N'-diethylformamidine: N,N'-di 25 N-cyclohexyldiamidinomethane; N-norbornyldiamidi isopropylformamidine; N.N'-dibutyl formamidine: N,N'- nomethane, N-adamantyldiamidinomethane; dimethyldia diphenylformamidine: N,N'-dibenzylformamidine: N,N'- midinomethane; diethyldiamidinomethane; diisopropyldia dinaphthylformamidine; N.N'-dicyclohexylformamidine: midinomethane; dibutyldiamidinomethane: N,N'-dinorbornylformamidine: N,N'-diadamantylformami dibenzyldiamidinomethane; diphenyldiamidinomethane; dine: N,N'-dianthraquinonylformamidine: N,N-dimethylac 30 ditolyldiamidinomethane; dinaphthyldiamidinomethane; etamidine: N,N'-diethylacetamidine; N.N'-diisopropylaceta dicyclohexyldiamidinomethane; dinorbornyldiamidi midine; N,N'-dibutylacetamidine: N,N'- nomethane; diadamantyldiamidinomethane; ethylenebisdia diphenylacetamidine; N.N'-dibenzylacetamidine: N,N'- midinomethane; propylenebisdiamidinomethane; tetrameth dinaphthylacetamidine; N,N'-dicyclohexylacetamidine: ylenebisdiamidinomethane; N,N'-dinorbornylacetamidine: N,N'-diadamantylacetami 35 pentamethylenebisdiamidinomethane; hexamethylenebis dine; N,N-dimethylbenzamidine; N.N'-diethylbenzamidine: diamidinomethane; heptamethylenebisdiamidinomethane; N,N'-diisopropylbenzamidine: N,N'-dibutylbenzamidine: octamethylenebisdiamidinomethane; phenylenebisdiamidi N,N'-diphenylbenzamidine: N,N'-dibenzylbenzamidine: nomethane; piperazinebisdiamidinomethane; oxalylbisdia N,N'-dinaphthylbenzamidine; N,N'-dicyclohexylbenzami midinomethane; malonylbisdiamidinomethane; Succinylbis dine; N.N'-dinorbornylbenzamidine; N,N'-diadamantylben 40 diamidinomethane; glutarylbisdiamidinomethane; Zamidine: N,N'-dimethyltoluamidine: N,N'-diethyltoluami phthalylbisdiamidinomethane: 2-amidinomethylthiazole; dine; N,N'-diisopropyltoluamidine: N,N'- 2-amidinomethyloxazole; 2-amidinomethylimidazole; dibutyltoluamidine; N.N'-diphenyltoluamidine: N,N'- 3-amidinomethylpyrazole; 3-amidinomethyl-1,2,4-triazole; dibenzyltoluamidine: N,N'-dinaphthyltoluamidine: N,N'- and 5-amidinomethyltetrazole. dicyclohexyltoluamidine; N,N'-dinorbornyltoluamidine: 45 N Valence Stabilizer #21: Examples of imidoylguanidines, N,N'-diadamantyltoluamidine; oxalic diamidine: malonic amidinoguanidines, bis(imidoylguanidines), bis(amidi diamidine. Succinic diamidine; glutaric diamidine; adipic noguanidines), poly(imidoylguanidines), and poly(amidi diamidine; pimelic diamidine; Suberic diamidine; phthalic noguanidines) (N N bidentates, N N tridentates, N N diamidine; terephthalic diamidine; isophthalic diamidine; tetradentates, and N N hexadentates) that meet the require piperazine diamidine; 2-liminopyrrolidine: 2-iminopiperi 50 ments for use as “wide band” valence stabilizers for Mn' dine; amidinobenzamide; benzamidine; chloroaZodin; and and/or Mn" include, but are not limited to: acetimi debrisoquin. doylguanidine; amidinoguanidine, benzimidoylguanidine; cyclohexylimidoylguanidine; pentafluorobenzimidoylguani NValence Stabilizer #19. Examples of biguanides (imidodi dine, 2-N-imidoylaminothiazole; 2-N-imidoylaminoox carbonimidic diamides), biguanidines, imidotricarbonimidic 55 azole: 2-N-imidoylaminoimidazole;3-N-imidoylaminopyra diamides, imidotetracarbonimidic diamides, dibiguanides, Zole; 3-N-imidoylamino-1,2,4-triazole; and 5-N- bis(biguanidines), polybiguanides, and poly(biguanidines) imidoylaminotetrazole. (N N bidentates, N N tridentates, N N tetradentates, and N N hexadentates) that meet the requirements for use as NValence Stabilizer #22: Examples of diformamidine oxides “wide band valence stabilizers for Mn" and/or Mn" 60 (dicarbonimidic diamides), tricarbonimidic diamides, tetra include, but are not limited to:biguanide (bigH); biguanidine, carbonimidic diamides, bis(diformamidine oxides), and poly methylbiguanide; ethylbiguanide; isopropylbiguanide; (diformamidine oxides) (N N bidentates, N N tridentates, butylbiguanide; benzylbiguanide; phenylbiguanide; tolyl or N N tetradentates) that meet the requirements for use as biguanide; naphthylbiguanide; cyclohexylbiguanide; nor “wide band valence stabilizers for Mn" and/or Mn" bornylbiguanide; adamantylbiguanide; dimethylbiguanide; 65 include, but are not limited to: diformamidine oxide; meth diethylbiguanide; diisopropylbiguanide; dibutylbiguanide; yldiformamidine oxide; ethyldiformamidine oxide: isopro dibenzylbiguanide; diphenylbiguanide; ditolylbiguanide; pyldiformamidine oxide; butyldiformamidine oxide; ben US 7,789,958 B2 95 96 Zyldiformamidine oxide; phenyldiformamidine oxide: requirements for use as “wide band valence stabilizers for tolyldiformamidine oxide; naphthyldiformamidine oxide: Mn" and/or Mn" include, but are not limited to: thioimi cyclohexyldiformamidine oxide; norbornyldiformamidine dodicarbonimidic acid, thiodiimidodicarbonimidic acid, oxide; adamantyldiformamidine oxide; dimethyldiformami thioimidotricarbonimidic acid, thioimidotetracarbonimidic dine oxide; diethyldiformamidine oxide; diisopropyldifor- 5 acid; O-methylthioimidodicarbonimidic acid; O-ethylthio mamidine oxide: dibutyldiformamidine oxide: dibenzyldi imidodicarbonimidic acid; O-isopropylthioimidodicarboni formamidine oxide: diphenyldiformamidine oxide: midic acid; O-phenylthioimidodicarbonimidic acid; O-ben ditolyldiformamidine oxide; dinaphthyldiformamidine Zylthioimidodicarbonimidic acid; oxide; dicyclohexyldiformamidine oxide; dinorbornyldifor O-cyclohexylthioimidodicarbonimidic acid; O-naphthylth mamidine oxide; diadamantyldiformamidine oxide: 2-O- 10 ioimidodicarbonimidic acid; O-norbornylthioimidodicar amidinohydroxythiazole; 2-O-amidinohydroxyoxazole; bonimidic acid; O-adamantylthioimidodicarbonimidic acid; 2-O-amidinohydroxyimidazole; 3-O-amidinohydroxypyra O.O'-dimethylthioimidodicarbonimidic acid; O,O'-dieth Zole: 3-O-amidinohydroxy-1,2,4-triazole; and 5-O-amidino ylthioimidodicarbonimidic acid; O,O'-diisopropylthioimi hydroxytetrazole. dodicarbonimidic acid; O,O'-diphenylthioimidodicarbonim 15 idic acid; O,O'-dibenzylthioimidodicarbonimidic acid; O,O'- N Valence Stabilizer #23: Examples of diformamidine sul dicyclohexylthioimidodicarbonimidic acid; O,O'- fides (thiodicarbonimidic diamides), thiotricarbonimidic dia dinaphthylthioimidodicarbonimidic acid; O,O'- mides, thiotetracarbonimidic diamides, bis(diformamidine dinorbornylthioimidodicarbonimidic acid; and O,O'- sulfides), and poly(diformamidine sulfides) (N N biden diadamantylthioimidodicarbonimidic acid. tates, N N tridentates, or N N tetradentates) that meet the 20 requirements for use as “wide band valence stabilizers for N Valence Stabilizer #26: Examples of diimidoylimines, Mn" and/or Mn' include, but are not limited to: diformami diimidoylhydrazides, bis(diimidoylimines), bis(diimidoyl dine sulfide; methyldiformamidine sulfide; ethyldiformami hydrazides), poly(diimidoylimines), and poly(diimidoylhy dine sulfide: isopropyldiformamidine sulfide; butyldiforma drazides) (N N Tridentates and N N Hexadentates) that midine sulfide; benzyldiformamidine sulfide; 25 meet the requirements for use as “wide band valence stabi phenyldiformamidine sulfide; tolyldiformamidine sulfide: lizers for Mn" and/or Mn" include, but are not limited to: naphthyldiformamidine sulfide; cyclohexyldiformamidine diacetimidoylimine; dibenzimidoylimine; and dicyclohexy sulfide; norbornyldiformamidine sulfide; adamantyldiforma limidoylimine. midine sulfide; dimethyldiformamidine sulfide; diethyldifor N Valence Stabilizer #27: Examples of imidosulfamides, mamidine sulfide; diisopropyldiformamidine sulfide: dibu- 30 diimidosulfamides, bis(imidosulfamides), bis(diimidosulfa tyldiformamidine sulfide: dibenzyldiformamidine sulfide: mides), poly(imidosulfamides), and poly(diimidosulfa diphenyldiformamidine sulfide; ditolyldiformamidine sul mides) (N N Bidentates, N N Tridentates, N N Tet fide; dinaphthyldiformamidine sulfide; dicyclohexyldifor radentates, and N N Hexadentates) that meet the mamidine sulfide; dinorbornyldiformamidine sulfide; diada requirements for use as “wide band valence stabilizers for mantyldiformamidine sulfide: phenylthiobisformamidine: 35 Mn" and/or Mn" include, but are not limited to: imidosul 2-S-amidinomercaptothiazole; 2-S-amidinomercaptooX famidic acid, diimidosulfamidic acid; O-phenylimidosulfa azole; 2-S-amidinomercaptoimidazole; 3-S-amidinomercap mide: O-benzylimidosulfamide: N-phenylimidosulfamide: topyrazole; 3-S-amidinomercapto-1,2,4-triazole; and 5-S- N-benzylimidosulfamide: O-phenyldiimidosulfamide: amidinomercaptotetrazole. O-benzyldiimidosulfamide: N-phenyldiimidosulfamide; and N-benzyldiimidosulfamide. NValence Stabilizer #24: Examples of imidodicarbonimidic 40 acids, diimidodicarbonimidic acids, imidotricarbonimidic NValence Stabilizer #28: Examples of phosphoramidimidic acids, imidotetracarbonimidic acids, and derivatives thereof triamides, bis(phosphoramidimidic triamides), and poly (N N Bidentates, N N Tridentates, N N Tetradentates, (phosphoramidimidic triamides) and derivatives thereof and N N Hexadentates) that meet the requirements for use (N N Bidentates, N N Tridentates, N N Tetradentates, as “wide band valence stabilizers for Mn" and/or Mn" 45 and N N Hexadentates) that meet the requirements for use include, but are not limited to: imidodicarbonimidic acid, as “wide band' valence stabilizers for Mn" and/or Mn" diimidodicarbonimidic acid, imidotricarbonimidic acid, imi include, but are not limited to: phosphoramidimidic triamide; dotetracarbonimidic acid; O-methylimidodicarbonimidic N-phenylphosphoramidimidic triamide, N-benzylphos acid; O-ethylimidodicarbonimidic acid; O-isopropylimi phoramidimidic triamide: N-naphthylphosphoramidimidic dodicarbonimidic acid; O-phenylimidodicarbonimidic acid; 50 triamide: N-cyclohexylphosphoramidimidic triamide: O-benzylimidodicarbonimidic acid; O-cyclohexylimidodi N-norbornylphosphoramidimidic triamide: N,N'-diphe carbonimidic acid; O-naphthylimidodicarbonimidic acid; nylphosphoramidimidic triamide: N,N'-dibenzylphosphora O-norbornylimidodicarbonimidic acid; O-adamanty limi midimidic triamide: N,N'-dinaphthylphosphoramidimidic dodicarbonimidic acid; O,O'-dimethylimidodicarbonimidic triamide: N,N'-dicyclohexylphosphoramidimidic triamide: acid; O,O'-diethylimidodicarbonimidic acid; O,O'-diisopro 55 and N,N'-dinorbornylphosphoramidimidic triamide. pylimidodicarbonimidic acid; O,O'-diphenylimidodicar bonimidic acid; O,O'-dibenzylimidodicarbonimidic acid; NValence Stabilizer #29. Examples of phosphoramidimidic O.O'-dicyclohexylimidodicarbonimidic acid; O,O'-dinaph acid, phosphorodiamidimidic acid, bis(phosphoramidimidic thylimidodicarbonimidic acid; O,O'-dinorbornylimidodicar acid), bis(phosphorodiamidimidic acid), poly(phosphorami 60 dimidic acid), poly(phosphorodiamidimidic acid), and bonimidic acid; and O,O'-diadamanty limidodicarbonimidic derivatives thereof (N N Bidentates, N N Tridentates, acid. N N Tetradentates, and N N Hexadentates) that meet the NValence Stabilizer #25: Examples of thioimidodicarboni requirements for use as “wide band valence stabilizers for midic acids, thiodiimidodicarbonimidic acids, thioimidotri Mn" and/or Mn' include, but are not limited to: phosphora carbonimidic acids, thioimidotetracarbonimidic acids, and 65 midimidic acid, phosphorodiamidimidic acid, O-phe derivatives thereof (N N Bidentates, N N Tridentates, nylphosphoramidimidic acid; O-benzylphosphoramidimidic N N Tetradentates, and N N Hexadentates) that meet the acid; O-naphthylphosphoramidimidic acid; O-cyclohexy US 7,789,958 B2 97 98 lphosphoramidimidic acid; O-norbornylphosphoramidim diaZeneformimidic acid, diphenyldiazeneformimidic acid, idic acid; O,O'-diphenylphosphoramidimidic acid; O,O'- phenyldiazeneacetimidic acid, and diphenyldiaZeneacetim dibenzylphosphoramidimidic acid; O,O'- idic acid. dinaphthylphosphoramidimidic acid; O,O'- dicyclohexylphosphoramidimidic acid; and O,O'- N Valence Stabilizer #34: Examples of diazeneformimidot dinorbornylphosphoramidimidic acid. hioic acid, diaZeneacetimidothioic acid, bis(diazeneformim idothioic acid), bis(diazeneacetimidothioic acid), poly(diaz N Valence Stabilizer #30: Examples of phosphoramidimi eneformimidothioic acid), poly(diazeneacetimidothioic dodithioic acid, phosphorodiamidimidothioic acid, bis(pho acid), and derivatives thereof (N N Bidentates, N N Tet sphoramidimidodithioic acid), bis(phosphorodiamidimidot 10 radentates, and N N Hexadentates) that meet the require hioic acid), poly(phosphoramidimidodithioic acid), poly ments for use as “wide band valence stabilizers for Mn" (phosphorodiamidimidothioic acid), and derivatives thereof and/or Mn" include, but are not limited to: diazeneformim (N N Bidentates, N N Tridentates, N N Tetradentates, idothioic acid, diaZeneacetimidothioic acid, phenyldiazene and N N Hexadentates) that meet the requirements for use formimidothioic acid, diphenyldiaZeneformimidothioic acid, as “wide band' valence stabilizers for Mn" and/or Mn" 15 phenyldiazeneacetimidothioic acid, and diphenyldiaZeneace include, but are not limited to: phosphoramidimidodithioic timidothioic acid. acid, phosphorodiamidimidothioic acid, S-phenylphosphora midimidodithioic acid: S-benzylphosphoramidimidodithoic NValence Stabilizer #35: Examples of imidoyldiazenes, bis acid; S-naphthylphosphoramidimidodithioic acid; S-cyclo (imidoyldiazenes), and poly(imidoyldiazenes), (N N Tri hexylphosphoramidimidodithioic acid: S-norbornylphos dentates and N N Hexadentates) that meet the requirements phoramidimidodithioic acid: S.S'-diphenylphosphorami for use as “wide band valence stabilizers for Mn" and/or dimidodithioic acid; S.S.- Mn' include, but are not limited to: acetimidoyldiazene: dibenzylphosphoramidimidodithioic acid; S.S.- benzimidoyldiaZene; and cyclohexylimidoyldiazene. dinaphthylphosphoramidimidodithioic acid; S.S.- NValence Stabilizer #36: Examples of diazenediformimida dicyclohexylphosphoramidimidodithioic acid; and S.S.- 25 mides (1,2-diazenediamidines), diaZenediacetimidamides dinorbornylphosphoramidimidodithioic acid. (1,2-diazene-di-alpha-amidinoalkanes(alkenes)), bis(diaz NValence Stabilizer #31: Examples of azo compounds with enediformimidamides), bis(diazenediacetimidamides), poly amino, imino, oximo, diaZeno, or hydrazido Substitution at (diaZenediformimidamides), and poly(diazenediacetimida the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, 30 mides) (N N Tridentates and N N Hexadentates) that biso-(HN ) or alpha- or beta-(HN-)aZo compounds, or meet the requirements for use as “wide band valence stabi polyo-(HN ) or alpha- or beta-(HN-)azo compounds) lizers for Mn" and/or Mn" include, but are not limited to: (N N Bidentates, N N Tridentates, N N Tetradentates, diaZenediformimidamide (1,2-diazenediamidine), diaZene or N N Hexadentates) that meet the requirements for use as diacetimidamide (1,2-diazene-di-alpha-amidinomethane); “wide band' valence stabilizers for Mn" and/or Mn" 35 diphenyldiazenediformimidamide; tetraphenyldiazenedi include, but are not limited to: o-aminoaZobenzene, o.o'- formimidamide; diphenyldiazenediacetimidamide; and tet diaminoaZobenzene; (2-pyridine)aZobenzene: 1-phenylaZo raphenyldiazenediacetimidamide. 2-naphthylamine; pyridineaZo-2-naphthol (PAN); pyridinea Zoresorcinol (PAR); o-hydroxy-o'-(beta-aminoethylamino) NValence Stabilizer #37: Examples of diazenediformimidic azobenzene: Benzopurpurin 4B: Congo Red; Fat Brown RR: 40 acid, diaZenediacetimidic acid, bis(diaZenediformimidic benzopurpurin; Congo Red; Direct Red 75; Mordant Brown acid), bis(diaZenediacetimidic acid), poly(diazenediformim 48: Nitro Red; 2-imidazolylazobenzene: 2-benzimidazolyla idic acid), and poly(diazenediacetimidic acid), and deriva Zobenzene: 3-pyrazolylazobenzene: 3-(1,2,4-triazolyl) tives thereof (N N Tridentates and N N Hexadentates) aZobenzene: 2-pyridylazobenzene: 2-pyrazinylazobenzene: that meet the requirements for use as “wide band valence and 2-pyrimidinylazobenzene. 45 stabilizers for Mn" and/or Mn" include, but are not limited to: diaZenediformimidic acid, diaZenediacetimidic acid, N Valence Stabilizer #32: Examples of diazeneformimida diphenyldiazenediformimidic acid, and diphenyldiazenedi mides (diazeneamidines), diaZeneacetimidamides (diazene alpha-amidinoalkanes(alkenes)), bis(diazeneformimida acetimidic acid. mides), bis(diazeneacetimidamides), poly NValence Stabilizer #38: Examples of diazenediformimidot (diaZeneformimidamides), and poly 50 hioic acid, diaZenediacetimidothioic acid, bis(diazenedi (diazeneacetimidamides) (N N Bidentates, N N formimidothioic acid), bis(diaZenediacetimidothioic acid), Tetradentates, and N N Hexadentates) that meet the poly(diazenediformimidothioic acid), and poly(diazenedi requirements for use as “wide band valence stabilizers for acetimidothioic acid), and derivatives thereof (N N Triden Mn" and/or Mn' include, but are not limited to: diazene tates and N N Hexadentates) that meet the requirements for formimidamide (diaZeneamidine); diaZeneacetimidamide 55 use as “wide band valence stabilizers for Mn" and/or Mn" (diazene-alpha-amidinomethane); phenyldiaZeneformimida include, but are not limited to: diazenediformimidothioic mide; triphenyldiaZeneformimidamide; phenyldiazeneace acid, diaZenediacetimidothioic acid, diphenyldiazenedi timidamide; and triphenyldiazeneacetimidamide. formimidothioic acid, and diphenyldiazenediacetimidothioic acid. N Valence Stabilizer #33: Examples of diazeneformimidic 60 acid, diaZeneacetimidic acid, bis(diazeneformimidic acid), N Valence Stabilizer #39: Examples of diimidoyldiazenes, bis(diazeneacetimidic acid), poly(diaZeneformimidic acid), bis(diimidoyldiazenes), and poly(diimidoyldiaZenes), poly(diazeneacetimidic acid), and derivatives thereof (N N (N N Tridentates and N N Hexadentates) that meet the Bidentates, N N Tetradentates, and N N Hexadentates) requirements for use as “wide band valence stabilizers for that meet the requirements for use as “wide band valence 65 Mn" and/or Mn' include, but are not limited to: diacetimi stabilizers for Mn" and/or Mn" include, but are not limited doyldiazene, dibenzimidoyldiazene, and dicyclohexylimi to: diaZeneformimidic acid, diaZeneacetimidic acid, phenyl doyldiazene. US 7,789,958 B2 99 100 NValence Stabilizer #40. Examples of ortho-amino (or -hy aniline; N.N'-(Formylcamphoro)di-aminonorborname: N,N'- drazido) Substituted formazans, bis(o-amino or -hydrazido (Acetylacetonato)diisopropylamine; N.N'-(Acetylacetonato) Substituted formazans), and poly(o-amino or -hydrazido Sub dicyclohexylamine; N.N'-(Acetylacetonato)dianiline; N.N'- stituted formazans) (N N Bidentates, N N Tridentates, (Acetylacetonato)di-aminonorbornane; N,N'- N N Tetradentates, and N N Hexadentates) that meet the (Diacetylbenzeno)diisopropylamine; N,N'- requirements for use as “wide band valence stabilizers for (Diacetylbenzeno)dicyclohexylamine; N,N'- Mn" and/or Mn' include, but are not limited to: 1-(2-ami (Diacetylbenzeno)dianiline; N,N'-(Diacetylbenzeno)di nophenyl)-3,5-diphenylformazan, and 1.5-bis(2-aminophe aminonorbornane; N,N'-(1,2-Cyclohexanono) nyl)-3-phenylformazan. diisopropylamine; N,N'-(1,2-Cyclohexanono) 10 dicyclohexylamine; N,N'-(1,2-Cyclohexanono)dianiline: NValence Stabilizer #41: Examples of ortho-amino (or -hy N,N'-(1,2-Cyclohexanono)di-aminonorbornane; N,N'- drazido) Substituted azines (including ketazines), bis(o- (Camphorquinono)diisopropylamine; N,N'-(Cam amino or hydrazido Substituted azines), and poly(o-amino or phorquinono)dicyclohexylamine; N.N'-(Camphorquinono) hydrazido substituted azines) (N N Bidentates, N N Tri dianiline; N,N'-(Camphorquinono)di-aminonorbornane; dentates, N N Tetradentates, and N N Hexadentates) that 15 N,N'-(Benzaldehydo)ethylenediamine; N.N'-(Naphthalde meet the requirements for use as “wide band valence stabi hydo)ethylenediamine; N.N'-(Acetophenono)ethylenedi lizers for Mn" and/or Mn" include, but are not limited to: amine; N.N'-(Benzaldehydo)trimethylenediamine; N.N'- 2-amino-1-benzalazine; 2-amino-1-naphthalazine; and (Naphthaldehydo)trimethylenediamine; N,N'- 2-amino-1-cyclohexanonazine. (Acetophenono)trimethylenediamine; N.N'-(Benzaldehydo) NValence Stabilizer #42: Examples of Schiff Bases with one cyclohexane-1,2-diamine; N,N'-(Naphthaldehydo) Imine (C—N) Group and with ortho- or alpha- or beta-amino cyclohexane-1,2-diamine; N,N'-(Acetophenono) or imino or oximo or diaZeno or hydrazido Substitution cyclohexane-1,2-diamine; N,N'-(Benzaldehydo)-1,2- (N N Bidentates, N N Tridentates, N N Tetradentates, diaminobenzene: N,N'-(Naphthaldehydo)-1,2- N N Pentadentates, or N N Hexadentates) that meet the diaminobenzene: N,N'-(Acetophenono)-1,2- requirements for use as “wide band valence stabilizers for 25 diaminobenzene: N,N'-(Acetylacetonato)ethylenediamine: Mn" and/or Mn' include, but are not limited to: N-(2-Ami N,N'-(Acetylacetonato)-1,2-cyclohexylenediamine; N.N'- nobenzaldehydo)isopropylamine; N-(2-Pyridinecarboxalde (Acetylacetonato)-1,2-propylenediamine: N,N'-(Glyoxalo)- hydo)isopropylamine; N-(2-Pyrrollecarboxaldehydo)isopro o-phenylenediamine; and N,N'-(Glyoxalo)ethylenediamine. pylamine; N-(2-Acetylpyridino)isopropylamine, N-(2- Also includes dihydrazones. Acetylpyrrolo)isopropylamine; N-(2-Aminoacetophenono) 30 isopropylamine; N-(2-Aminobenzaldehydo) NValence Stabilizer #44: Examples of Schiff Bases with two cyclohexylamine; N-(2-Pyridinecarboxaldehydo) Imine (C=N) Groups and with ortho- or alpha- or beta cyclohexylamine; N-(2-Pyrrollecarboxaldehydo) amino orimino or oximo or diaZeno or hydrazido Substitution cyclohexylamine; N-(2-Acetylpyridino)cyclohexylamine; (N N Bidentates, N N Tridentates, N N Tetradentates, N-(2-Acetylpyrrolo)cyclohexylamine: N-(2-Aminoac 35 N N Pentadentates, or N N Hexadentates) that meet the etophenono)cyclohexylamine; N-(2-Aminobenzaldehydo) requirements for use as “wide band valence stabilizers for aniline; N-(2-Pyridinecarboxaldehydo)aniline; N-(2-Pyr Mn" and/or Mn" include, but are not limited to: N,N'-(2,6- rolecarboxaldehydo)aniline; N-(2-Acetylpyridino)aniline; Pyridinedicarboxaldehydo)diisopropylamine; N.N'-(2,6-Py N-(2-Acetylpyrrolo)aniline; N-(2-Aminoacetophenono) ridinedicarboxaldehydo)dicyclohexylamine; N.N'-(2,6-Py aniline; N-(2-Aminobenzaldehydo)aminonorbornane; N-(2- 40 ridinedicarboxaldehydo)dianiline; N,N'-(2,6- Pyridinecarboxaldehydo)aminonorborname: N-(2-Pyrrole Pyridinedicarboxaldehydo)di-aminonorborname: N,N'-(2,5- carboxaldehydo)aminonorbornane, N-(2-Acetylpyridino) Pyrroledicarboxaldehydo)diisopropylamine; N,N'-(2,5- aminonorbornane; N-(2-Acetylpyrrolo)aminonorborname: Pyrroledicarboxaldehydo)dicyclohexylamine; N.N'-(2,5- N-(2-Aminoacetophenono)aminonorbornane, 2-pyrrollecar Pyrroledicarboxaldehydo)dianiline; N,N'-(2,5- 45 Pyrroledicarboxaldehydo)di-aminonorborname: N,N'-(o- boxaldehyde phenylhydrazone: 2-pyrrollecarboxaldehyde Aminophthalicdialdehydo)diisopropylamine; N,N'-(o- 2-pyridyl hydraZone; 2-aminobenzaldehyde phenylhydra Aminophthalicdialdehydo)dicyclohexylamine: N,N'-(o- Zone (nitrin); and 2-aminobenzaldehyde 2-pyridyl hydra Aminophthalicdialdehydo)dianiline: N,N'-(o- Zone. Also includes hydrazones with ortho-N substitution. Aminophthalicdialdehydo)di-aminonorbornane; N.N'-(o- NValence Stabilizer #43: Examples of Schiff Bases with two 50 Aminoformylcamphoro)diisopropylamine; N,N'-(o- Imine (C—N) Groups and without ortho- (for aryl constitu Aminoformylcamphoro)dicyclohexylamine; N,N'-(o- ents) or alpha- or beta- (for alkyl constituents) hydroxy, car Aminoformylcamphoro)dianiline; N,N'-(o- boxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, Aminoformylcamphoro)di-aminonorbornane; N.N'-(2,6- oximo, diazeno, or hydrazido substitution (N. NBidentates) Diacetylpyridino)diisopropylamine; N,N'-(2,6- that meet the requirements for use as “wide band valence 55 Diacetylpyridino)dicyclohexylamine; N,N'-(2,6- stabilizers for Mn" and/or Mn" include, but are not limited Diacetylpyridino)dianiline; N.N'-(2,6-Diacetylpyridino)di to: N,N'-(Glyoxalo)diisopropylamine; N.N'-(Glyoxalo)dicy aminonorbornane; N,N'-(o-Aminodiacetylbenzeno) clohexylamine; N.N'-(Glyoxalo)dianiline; N.N'-(Glyoxalo) diisopropylamine; N,N'-(o-Aminodiacetylbenzeno) di-aminonorborname: N,N'-(Malondialdehydo)diisopropy dicyclohexylamine; N,N'-(o-Aminodiacetylbenzeno) lamine: N,N'-(Malondialdehydo)dicyclohexylamine; N.N'- 60 dianiline; N,N'-(o-Aminodiacetylbenzeno)di (Malondialdehydo)dianiline: N,N'-(Malondialdehydo)di aminonorborname: N,N'-(3,6-Diamino-1,2-cyclohexanono) aminonorbornane; N,N'-(Phthalicdialdehydo) diisopropylamine; N.N'-(3,6-Diamino-1,2-cyclohexanono) diisopropylamine; N,N'-(Phthalicdialdehydo) dicyclohexylamine: N,N'-(3,6-Diamino-1,2-cyclohexanono) dicyclohexylamine; N,N'-(Phthalicdialdehydo)dianiline: dianiline; N,N'-(3,6-Diamino-1,2-cyclohexanono)di N,N'-(Phthalicdialdehydo)di-aminonorborname: N,N'- 65 aminonorbornane; N,N'-(2,5-Diacetylpyrrolo) (Formylcamphoro)diisopropylamine; N.N'-(Formylcam diisopropylamine; N,N'-(2,5-Diacetylpyrrolo) phoro)dicyclohexylamine; N,N'-(Formylcamphoro)di dicyclohexylamine; N.N'-(2,5-Diacetylpyrrolo)dianiline: US 7,789,958 B2 101 102 N,N'-(2,5-Diacetylpyrrolo)di-aminonorbornane; N.N'-(o- decane (15ane( -SH)); tetrathiolocycloeicosane (20ane Aminobenzaldehydo)ethylenediamine; N.N'-(o-Aminon (—SH)); tetrathiolocyclooctadecane (18 ane( -SH)); aphthaldehydo)ethylenediamine; N.N'-(o-Aminoacetophe tetrathiolocyclohexadecane (16ane( SH)); tetrathiolocy nono)ethylenediamine; N,N'-(o-Aminobenzaldehydo) clotetradecane (14ane( -SH)); tetrathiolocyclododecane trimethylenediamine; N,N'-(o-Aminonaphthaldehydo) (12ane( -SH)); dithiolocyclohexadecane (16ane trimethylenediamine; N,N'-(o-Aminoacetophenono) (—SH)); dithiolocyclotetraadecane (14ane( -SH)); trimethylenediamine; N,N'-(o-Aminobenzaldehydo) dithiolocyclododecane (12lane( SH)); dithiolocyclode cyclohexane-1,2-diamine; N.N'-(o-Aminonaphthaldehydo) cane (10ane( SH)); and dithiolocyclooctane (8 lane(- cyclohexane-1,2-diamine; N.N'-(o-Aminoacetophenono) SH)). cyclohexane-1,2-diamine; N.N'-(o-Aminobenzaldehydo)-1, 10 S Valence Stabilizer #3: Examples of dithioimidodialde 2-diaminobenzene: N,N'-(o-Aminonaphthaldehydo)-1,2- hydes, dithiohydrazidodialdehydes (thioacyl thiohy diaminobenzene, and N,N'-(o-Aminoacetophenono)-1,2- drazides), bis(dithioimidodialdehydes), bis(dithiohydrazi diaminobenzene. Also includes hydrazones with ortho-N dodialdehydes), poly(dithioimidodialdehydes), and poly substitution. (dithiohydrazidodialdehydes) (S–S Bidentates, S. S N Valence Stabilizer #45: Examples of Schiff Bases with 15 Tridentates, S S Tetradentates) that meet the requirements three Imine (C—N) Groups and without ortho- (for aryl con for use as “wide band valence stabilizers for Mn" and/or stituents) or alpha- or beta- (for alkyl constituents) hydroxy, Mn' include, but are not limited to: dithiodiacetamide, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, dithiodipropanamide, dithiodibutanamide, dithiodibenza imino, oximo, diazeno, or hydrazido substitution (N N Tri mide, and dithiodicyclohexamide. dentates) that meet the requirements for use as “wide band' valence stabilizers for Mn" and/or Mn" include, but are not SValence Stabilizer #4: Examples of dithioimidodicarbonic limited to: N,N',N'-(Benzaldehydo)tris(2-aminoethyl) acids, dithiohydrazidodicarbonic acids, bis(dithioimidodi amine; N.N',N'-(Naphthaldehydo)tris(2-aminoethyl)amine: carbonic acids), bis(dithiohydrazidodicarbonic acids), poly and N,N',N'-(Acetophenono)tris(2-aminoethyl)amine. Also (dithioimidodicarbonic acids), poly(dithiohydrazidodicar 25 bonic acids) and derivatives thereof (S S Bidentates, S. S includes trihydrazones. Tridentates, S S Tetradentates) that meet the requirements N Valence Stabilizer #46: Examples of Schiff Bases with for use as “wide band” valence stabilizers for Mn" and/or three Imine (C—N) Groups and with ortho- or alpha- or Mn" include, but are not limited to: dithioimidodicarbonic beta-amino or imino or oximo or diaZeno or hydrazido Sub acid, dithiohydrazidodicarbonic acid, O-phenyldithioimi stitution (N NTridentates, N N Tetradentates, N N Pen 30 dodicarbonic acid, O-benzyldithioimidodicarbonic acid, tadentates, or N N Hexadentates) that meet the require O-cyclohexyldithioimidodicarbonic acid, O-nor ments for use as “wide band” valence stabilizers for Mn' bornyldithioimidodicarbonic acid, O.O'-diphenyldithioimi and/or Mn" include, but are not limited to: N,N',N'-(o-Ami dodicarbonic acid, O.O'-dibenzyldithioimidodicarbonic nobenzaldehydo)tris(2-aminoethyl)amine; N.N',N'-(o-Ami acid, O.O'-dicyclohexyldithioimidodicarbonic acid, and nonaphthaldehydo)tris(2-aminoethyl)amine; and N,N',N'- 35 O.O'-norbornyldithioimidodicarbonic acid. (o-Aminoacetophenono)tris(2-aminoethyl)amine. S Valence Stabilizer #5. Examples of 1,3-dithioketones SValence Stabilizer #1: Examples of macrocyclic, macrobi (dithio-beta-ketonates), 1,3,5-trithioketones, bis(1,3- cyclic, and macropolycyclic oligothioketones (including cat dithioketones), and poly(1,3-dithioketones) (S–S Biden apinands, cryptands, cyclidenes, and sepulchrates) wherein tates, S S Tridentates, S S Tetradentates) that meet the all binding sites are composed of thioketones (especially in 40 requirements for use as “wide band valence stabilizers for the beta position) (S–S Bidentates, S S Tetradentates, and Mn" and/or Mn' include, but are not limited to: hexafluo S–S Hexadentates) that meet the requirements for use as ropentanedithione; 1,3-diphenyl-1,3-propanedithione: “wide band valence stabilizers for Mn" and/or Mn" thiobenzoylthiopinacolone: dithiocyclohexoylmethane: include, but are not limited to: hexathioketocyclotetracosane diphenylpentanetrithionate; tetramethylnonanetrithionate; (24ane(=S)); hexathioketocycloheneicosane (21 lane 45 hexafluoroheptanetrithionate; trifluoroheptanetrithionate; (—S)); hexathioketocyclooctadecane (18ane(=S)); 1-(2-thienyl)-1,3-butanedithione, 1-(2-naphthyl)-1,3-bu hexathioketocyclopentadecane (15ane(=S)); tetrathioke tanedithione, trifluorothioacetylthiocamphor, and 1.3-indan tocycloeicosane (20ane(=S)); tetrathioketocyclooctade dithione. cane (18 ane(=S)); tetrathioketocyclohexadecane (16 ane(=S)); tetrathioketocyclotetradecane (14ane(=S)); 50 S Valence Stabilizer #6: Examples of 1,2-dithioketones tetrathioketocyclododecane (12ane(=S)); dithioketocy (dithiolenes, dithio-alpha-ketonates), 1,2,3-trithioketones, clohexadecane (16ane(=S)); dithioketocyclotetraadecane dithiotropolonates, o-dithioquinones, bis(1,2-dithioketones), (14ane(=S)); dithioketocyclododecane (12ane(=S)); and poly(1,2-dithioketones) (S–S Bidentates, S S Triden dithioketocyclodecane (10ane(=S)); and dithioketocy tates, S S Tetradentates) that meet the requirements for use 55 as “wide band valence stabilizers for Mn" and/or Mn" clooctane (8ane(=S)). include, but are not limited to: dithiotropolone; 1.2- SValence Stabilizer #2: Examples of macrocyclic, macrobi dithiobenzoquinone (o-dithioquinone)(o-benzenedithiolate) cyclic, and macropolycyclic dithiolenes (including catapi (bdt); di-tert-butyl-1,2-dithiobenzoquinone; hexafluoro-1,2- nands, cryptands, cyclidenes, and sepulchrates) wherein all dithiobenzoquinone; 1,2-dithionaphthoduinone; 9.10 binding sites are composed of alpha-, alpha-dithiolenes 60 dithiophenanthroquinone; ethylenedithiolene (edt); (meaning two thiol groups on a single carbonatom in the ring) maleonitriledithiolene (mint); trifluoromethyldithiolene (tfa); (S S Bidentates, S S Tetradentates, and S S Hexaden carbomethoxydithiolene (cmt); trithionedithiolene (dmit); tates) that meet the requirements for use as “wide band toluenedithiolate (tdt); dithiomanaldehyde (propenethione valence stabilizers for Mn" and/or Mn' include, but are not thiolate)(pt); dithioacetylacetonate (SacSac); dijulo limited to: hexathiolocyclotetracosane (24ane( -SH)); 65 lidinedithiolene; 2.3-piperazinedithiolate; di(4-aminophe hexathiolocycloheneicosane (21 lane( SH)); hexathiolo nyl)dithiolene; dimercaptoisotrithione (dmit); cyclooctadecane (18 ane( SH)); hexathiolocyclopenta (4-octylphenyl)dithiolene: benzenetetrathiol: US 7,789,958 B2 103 104 tetrathiosquaric acid; trithiodeltic acid; pentathiocroconic bornyltrithiodicarbonic acid, O.O'-diphenyltrithiodicarbonic acid; dithiocroconic acid; hexathiorhodizonic acid; dithior acid, O.O'-dibenzyltrithiodicarbonic acid, O.O'-dicyclohexy hodizonic acid; ethylenetetrathiol: trans-butadienetetrathi ltrithiodicarbonic acid, and O.O'-dinorbornyltrithiodicar olate; tetrathiooxalic acid; 1.2-indandithione; naphthothio bonic acid. quinone; acenapthenethioquinone; aceanthrenethioquinone; SValence Stabilizer #12: Examples of dithiohypophosphoric and indole-2,3-dithione (thioisatin). acids, bis(dithiohypophosphoric acids), poly(dithiohypo S Valence Stabilizer #7: Examples of dithiomalonamides phosphoric acids), and derivatives thereof (S–S Bidentates, S–S Tridentates, S S Tetradentates) that meet the require (dithiomalonodiamides), bis(dithiomalonamides), and poly ments for use as “wide band valence stabilizers for Mn" dithiomalonamides (S-S Bidentates, S S Tridentates, 10 S–S Tetradentates) that meet the requirements for use as and/or Mn' include, but are not limited to: dithiohypophos “wide band' valence stabilizers for Mn" and/or Mn" phoric acid, methyldithiohypophosphoric acid, isopropy include, but are not limited to: dithiomalonamide, N-phe ldithiohypophosphoric acid, tert-butyldithiohypophosphoric nyldithiomalonamide, N-benzyldithiomalonamide, N-pen acid, phenyldithiohypophosphoric acid, pentafluorophe tafluorophenyldithiomalonamide, N-cyclohexyldithioma 15 nyldithiohypophosphoric acid, benzyldithiohypophosphoric lonamide, N-norbornyldithiomalonamide, N,N'- acid, cyclohexyldithiohypophosphoric acid, O diphenyldithiomalonamide, N,N'- bornyldithiohypophosphoric acid, dimethyldithiohypophos dibenzyldithiomalonamide, N,N'- phoric acid, diisopropyldiothiohypophosphoric acid, di-tert dipentafluorophenyldithiomalonamide, N,N'- butyldithiohypophosphoric acid, dicyclohexyldithiomalonamide, and N,N'- diphenyldithiohypophosphoric acid, di-pentafluorophe norbornyldithiomalonamide. nyldithiohypophosphoric acid, dibenzyldithiohypophospho ric acid, dicyclohexyldithiohypophosphoric acid, and dinor S Valence Stabilizer #8: Examples of 2-thioacylthioaceta bornyldithiohypophosphoric acid. mides, bis(2-thioacylthioacetamides), and poly(2-thioacylth S Valence Stabilizer #13: Examples of dithiohypophos ioacetamides) (S SBidentates, S S Tridentates, S S Tet 25 phoramides, bis(dithiohypophosphoramides), and poly radentates) that meet the requirements for use as “wide band (dithiohypophosphoramides) (S S Bidentates, S S Tri valence stabilizers for Mn" and/or Mn' include, but are not dentates, S S Tetradentates) that meet the requirements for limited to: 2-thioacetothioacetamide, N-phenyl-2-thioac use as “wide band valence stabilizers for Mn" and/or Mn" etothioacetamide, N-pentafluorophenyl-2-thioacetothioac include, but are not limited to: dithiohypophosphoramide, etamide, N-benzyl-2-thioacetothioacetamide, N-cyclohexyl 30 N-methyldithiohypophosphoramide, N-isopropyldithiohy 2-thioacetothioacetamide, N-norbornyl-2- pophosphoramide, N-tert-butyldithiohypophosphoramide, thioacetothioacetamide, N-phenyl-2- N-phenyldithiohypophosphoramide, N-pentafluorophe thiobenzothioacetamide, N-pentafluorophenyl-2- nyldithiohypophosphoramide, N-benzyldithiohypophos pentafluorothiobenzothioacetamide, and N-cyclohexyl-2- phoramide, N-cyclohexyldithiohypophosphoramide, N-nor thiocyclohexothioacetamide. 35 bornyldithiohypophosphoramide, N,N"- SValence Stabilizer #9: Examples of dithioacyl sulfides, bis dimethyldithiohypophosphoramide, N,N"- (dithioacyl sulfides), and poly(dithioacyl sulfides), (S–S diisopropyldithiohypophosphoramide, N,N'-di-tert Bidentates, S S Tridentates, S S Tetradentates) that meet butyldithiohypophosphoramide, N,N"- the requirements for use as “wide band valence stabilizers diphenyldithiohypophosphoramide, N,N'-di for Mn" and/or Mn" include, but are not limited to: dithio 40 pentafluorophenyldithiohypophosphoramide, N,N"- acetyl sulfide; dithiopropanoyl sulfide; dithiobenzoyl sulfide: dibenzyldithiohypophosphoramide, N,N"- and dithiopentafluorobenzoyl sulfide. dicyclohexyldithiohypophosphoramide, and N,N"- dinorbornyldithiohypophosphoramide. SValence Stabilizer #10: Examples of trithiodicarbonic dia mides, bis(trithiodicarbonic diamides), and poly(trithiodicar S Valence Stabilizer #14: Examples of dithioimidodiphos bonic diamides) (S–S Bidentates, S S Tridentates, S. S 45 phoric acids, dithiohydrazidodiphosphoric acids, bis(dithio Tetradentates) that meet the requirements for use as “wide imidodiphosphoric acids), bis(dithiohydrazidodiphosphoric band valence stabilizers for Mn" and/or Mn" include, but acids), poly(dithioimidodiphosphoric acids), poly(dithiohy are not limited to: trithiodicarbonic diamide: N-phenyl drazidodiphosphoric acids), and derivatives thereof (S S trithiodicarbonic diamide: N-pentafluorophenyltrithiodi Bidentates, S S Tridentates, S S Tetradentates) that meet carbonic diamide: N-benzyltrithiodicarbonic diamide: N-cy 50 the requirements for use as “wide band valence stabilizers clohexyltrithiodicarbonic diamide: for Mn" and/or Mn" include, but are not limited to: dithio N-norbornyltrithiodicarbonic diamide: N,N'-diphenyl imidodiphosphoric acid, methyldithioimidodiphosphoric trithiodicarbonic diamide: N,N'-dipentafluorophenyl acid, isopropyldithioimidodiphosphoric acid, tert-bu trithiodicarbonic diamide: N,N'-dibenzyltrithiodicarbonic tyldithioimidodiphosphoric acid, phenyldithioimidodiphos diamide: N,N'-dicyclohexyltrithiodicarbonic diamide; and 55 phoric acid, pentafluorophenyldithioimidodiphosphoric acid, N,N'-dinorbornyltrithiodicarbonic diamide. benzyldithioimidodiphosphoric acid, cyclohexyldithioimi dodiphosphoric acid, norbornyldithioimidodiphosphoric SValence Stabilizer #11: Examples of pentathio-, tetrathio acid, dimethyldithioimidodiphosphoric acid, diisopropyldio or trithiodicarbonic acids, bis(pentathio-, tetrathio-, or thioimidodiphosphoric acid, di-tert-butyldithioimidodiphos trithiodicarbonic acids), poly(pentathio-, tetrathio-, or 60 phoric acid, diphenyldithioimidodiphosphoric acid, di-pen trithiodicarbonic acids), and derivatives thereof (S. S. Biden tafluorophenyldithioimidodiphosphoric acid, tates, S S Tridentates, S S Tetradentates) that meet the dibenzyldithioimidodiphosphoric acid, dicyclohexyldithio requirements for use as “wide band valence stabilizers for imidodiphosphoric acid, and dinorbornyldithioimidodiphos Mn" and/or Mn' include, but are not limited to: pentathiodi phoric acid. carbonic acid, tetrathiodicarbonic acid, trithiodicarbonic 65 acid, O-phenyltrithiodicarbonic acid, O-benzyltrithiodicar S Valence Stabilizer #15: Examples of dithioimidodiphos bonic acid, O-cyclohexyltrithiodicarbonic acid, O-nor phoramides, dithiohydrazidodiphosphoramides, bis(dithio US 7,789,958 B2 105 106 imidodiphosphoramides), bis(dithiohydrazidodiphosphora acid, O.S.-dicyclohexyltrithiophosphoric acid, and O.S.-di mides), poly(dithioimidodiphosphoramides), and poly norbornyltrithiophosphoric acid. (dithiohydrazidodiphosphoramides) (S–S Bidentates, S. S Tridentates, S S Tetradentates) that meet the requirements SValence Stabilizer #19. Examples of dithiophosphoric acids for use as “wide band valence stabilizers for Mn" and/or 5 (phosphorodithioic acids), bis(dithiophosphoric acids), poly Mn' include, but are not limited to: dithioimidodiphosphora (dithiophosphoric acids), and derivatives thereof (S–S mide, N-methyldithioimidodiphosphoramide, N-isopropy Bidentates, S S Tridentates, S S Tetradentates) that meet ldithioimidodiphosphoramide, N-tert-butyldithioimido the requirements for use as “wide band valence stabilizers diphosphoramide, N-phenyldithioimidodiphosphoramide, for Mn" and/or Mn" include, but are not limited to: dithio 10 phosphoric acid, O-phenyldithiophosphoric acid, O-ben N-pentafluorophenyldithioimidodiphosphoramide, N-ben Zyldithiophosphoric acid, O-cyclohexyldithiophosphoric Zyldithioimidodiphosphoramide, N-cyclohexyldithioimido acid, O-norbornyldithiophosphoric acid, O.O-diphe diphosphoramide, N-norbornyldithioimidodiphos nyldithiophosphoric acid, O.O-dibenzyldithiophosphoric phoramide, N.N"-dimethyldithioimidodiphosphoramide, acid, O.O-dicyclohexyldithiophosphoric acid, and O.O-di N.N"-diisopropyldithioimidodiphosphoramide, N,N'-di 15 norbornyldithiophosphoric acid. tert-butyldithioimidodiphosphoramide, N.N"-diphe nyldithioimidodiphosphoramide, N,N'-di-pentafluorophe S Valence Stabilizer #20. Examples of tetrathiophosphoric nyldithioimidodiphosphoramide, N,N'- acids (phosphorotetrathioic acids), bis(tetrathiophosphoric dibenzyldithioimidodiphosphoramide, N,N'- acids), poly(tetrathiophosphoric acids), and derivatives dicyclohexyldithioimidodiphosphoramide, and N.N"- thereof (S-S Bidentates, S S Tridentates, S S Tetraden dinorbornyldithioimidodiphosphoramide. tates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but are not S Valence Stabilizer #16: Examples of dithiodiphosphora limited to: tetrathiophosphoric acid, S-phenyltetrathiophos mides, bis(dithiodiphosphoramides), and poly(dithiodiphos phoric acid, S-benzyltetrathiophosphoric acid, S-cyclohexy ltetrathiophosphoric acid, S-norbornyltetrathiophosphoric phoramides) (S S Bidentates, S S Tridentates, S S Tet 25 radentates) that meet the requirements for use as “wide band acid, S.S.-diphenyltetrathiophosphoric acid, S.S.-diben valence stabilizers for Mn" and/or Mn" include, but are not Zyltetrathiophosphoric acid, S.S.-dicyclohexyltetrathiophos limited to: dithiodiphosphoramide, N-methyldithiodiphos phoric acid, and S.S.-dinorbornyltetrathiophosphoric acid. phoramide, N-isopropyldithiodiphosphoramide, N-tert-bu SValence Stabilizer #21: Examples of phosphoro(dithioper tyldithiodiphosphoramide, N-phenyldithiodiphosphora 30 oxo)dithioic acids, bisphosphoro(dithioperoxo)dithioic mide, N-pentafluorophenyldithiodiphosphoramide, acids, polyphosphoro(dithioperoxo)dithioic acids, and N-benzyldithiodiphosphoramide, N-cyclohexyldithio derivatives thereof (S–S Bidentates, S STridentates, S. S diphosphoramide, N-norbornyldithiodiphosphoramide, Tetradentates) that meet the requirements for use as “wide N,N'-dimethyldithiodiphosphoramide, N.N"-diisopropy band valence stabilizers for Mn" and/or Mn" include, but ldithiodiphosphoramide, N,N'-di-tert-butyldithiodiphos 35 are not limited to: phosphoro(dithioperoxo)dithioic acid, phoramide, N.N"-diphenyldithiodiphosphoramide, N.N"- O-phenylphosphoro(dithioperoxo)dithioic acid, O-ben di-pentafluorophenyldithiodiphosphoramide, N,N'- Zylphosphoro(dithioperoxo)dithioic acid, O-cyclohexy dibenzyldithiodiphosphoramide, N,N'- lphosphoro(dithioperoxo)dithioic acid, O-norbornylphos dicyclohexyldithiodiphosphoramide, and N,N'- phoro(dithioperoxo)dithioic acid, O.S.-diphenylphosphoro dinorbornyldithiodiphosphoramide. 40 (dithioperoxo)dithioic acid, O.S.-dibenzylphosphoro (dithioperoxo)dithioic acid, O.S.-dicyclohexylphosphoro S Valence Stabilizer #17: Examples of dithiodiphosphoric (dithioperoxo)dithioic acid, and O.S.-dinorbornylphosphoro acids, bis(dithiodiphosphoric acids), poly(dithiodiphospho (dithioperoxo)dithioic acid. ric acids), and derivatives thereof (S S Bidentates, S. S Tridentates, S S Tetradentates) that meet the requirements SValence Stabilizer #22: Examples of phosphoro(dithioper for use as “wide band” valence stabilizers for Mn" and/or 45 OXO)thioic acids, bisphosphoro(dithioperoxo)thioic acids. Mn" include, but are not limited to: dithiodiphosphoric acid, polyphosphoro(dithioperoxo)thioic acids, and derivatives methyldithiodiphosphoric acid, isopropyldithiodiphosphoric thereof (S-S Bidentates, S S Tridentates, S S Tetraden acid, tert-butyldithiodiphosphoric acid, phenyldithiodiphos tates) that meet the requirements for use as “wide band phoric acid, pentafluorophenyldithiodiphosphoric acid, ben valence stabilizers for Mn" and/or Mn" include, but are not Zyldithiodiphosphoric acid, cyclohexyldithiodiphosphoric 50 limited to: phosphoro(dithioperoxo)thioic acid, O-phe acid, norbornyldithiodiphosphoric acid, dimethyldithio nylphosphoro(dithioperoxo)thioic acid, O-benzylphosphoro diphosphoric acid, diisopropyldiothiodiphosphoric acid, di (dithioperoxo)thioic acid, O-cyclohexylphosphoro(dithiop tert-butyldithiodiphosphoric acid, diphenyldithiodiphospho eroxo)thioic acid, O-norbornylphosphoro(dithioperoxo) ric acid, di-pentafluorophenyldithiodiphosphoric acid, thioic acid, O.S.-diphenylphosphoro(dithioperoxo)thioic dibenzyldithiodiphosphoric acid, dicyclohexyldithiodiphos 55 acid, O.S.-dibenzylphosphoro(dithioperoxo)thioic acid, O.S.- phoric acid, and dinorbornyldithiodiphosphoric acid. dicyclohexylphosphoro(dithioperoxo)thioic acid, and O.S.- S Valence Stabilizer #18: Examples of trithiophosphoric dinorbornylphosphoro(dithioperoxo)thioic acid. acids (phosphorotrithioic acids), bis(trithiophosphoric SValence Stabilizer #23: Examples of phosphoro(dithioper acids), poly(trithiophosphoric acids), and derivatives thereof 60 oxo)trithioic acids, bisphosphoro(dithioperoxo)trithioic (S SBidentates, S S Tridentates, S S Tetradentates) that acids, polyphosphoro(dithioperoxo)trithioic acids, and meet the requirements for use as “wide band valence stabi derivatives thereof (S S Bidentates, S S Tridentates, S. S lizers for Mn" and/or Mn" include, but are not limited to: Tetradentates) that meet the requirements for use as “wide trithiophosphoric acid, O-phenyltrithiophosphoric acid, band valence stabilizers for Mn" and/or Mn" include, but O-benzyltrithiophosphoric acid, O-cyclohexyltrithiophos 65 are not limited to: phosphoro(dithioperoxo)trithioic acid, phoric acid, O-norbornyltrithiophosphoric acid, O.S.-diphe O-phenylphosphoro(dithioperoxo)trithioic acid, O-ben nyltrithiophosphoric acid, O.S.-dibenzyltrithiophosphoric Zylphosphoro(dithioperoxo)trithioic acid, O-cyclohexy US 7,789,958 B2 107 108 lphosphoro(dithioperoxo)trithioic acid, O-norbornylphos carboxylic acids), and derivatives thereof (S–S Bidentates phoro(dithioperoxo)trithioic acid, O.S.-diphenylphosphoro and S S Tetradentates) that meet the requirements for use as (dithioperoxo)trithioic acid, O.S.-dibenzylphosphoro “wide band' valence stabilizers for Mn" and/or Mn" (dithioperoxo)trithioic acid, O.S.-dicyclohexylphosphoro include, but are not limited to: dithioacetic acid; dithiopropi (dithioperoxo)trithioic acid, and O.S.-dinorbornylphosphoro onic acid; dithiobenzoic acid (dtb); dithiophenylacetic acid (dithioperoxo)trithioic acid. (dtpa); dithiocyclohexanoic acid; dithiofuroic acid; dithion SValence Stabilizer #24: Examples of beta-mercaptothioke aphthoic acid; phenyl dithioacetate; phenyl dithiopropionate; tones, beta-mercaptothioaldehydes, bis(beta-mercap phenyl dithiobenzoate; phenyl dithiocyclohexanoate; phenyl dithiofuroate; phenyl dithionaphthoate; tetrathiooxalic acid; tothioketones), bis(beta-mercaptothioaldehydes), poly(beta 10 mercaptothioketones), and poly(beta tetrathiomalonic acid; tetrathiosuccinic acid; trithiooxalic acid; trithiomalonic acid; trithiosuccinic acid; diphenyl mercaptothioaldehydes) (S–S Bidentates, S S Tridentates, tetrathiooxalate: diphenyl tetrathiomalonate; diphenyl S–S Tetradentates) that meet the requirements for use as tetrathiosuccinate; diphenyl trithiooxalate; diphenyl trithi “wide band' valence stabilizers for Mn" and/or Mn" omalonate; diphenyl trithiosuccinate; pyridine dithiocar include, but are not limited to: 4-mercaptopentan-2-thione; 15 1,3-diphenyl-3-mercaptopropanethioaldehyde; 1,3-diben boxylic acid; pyrrole dithiocarboxylic acid; thiophene dithio Zyl-3-mercaptopropanethioaldehyde; 1,3-dicyclohexyl-3- carboxylic acid; dithionaphthoic acid; and mercaptopropanethioaldehyde; 1,3-dinorbornyl-3-mercap tetrathiocamphonic acid. topropanethioaldehyde; 1,3-di(2-thienyl)-3- SValence Stabilizer #29. Examples of perthiomonocarboxy mercaptopropanethioaldehyde; 1,3-di(2-furyl)-3- lic acids, perthiodicarboxylic acids, bis(perthiomonocar mercaptopropanethioaldehyde; boxylic acids), bis(perthiodicarboxylic acids), poly(perthi o-mercaptothioacetophenone; 5-mercapto-1,4-dithionaph omonocarboxylic acids), poly(perthiodicarboxylic acids), thoduinone; 1-mercaptothioacridone; 1-mercaptodithioan and derivatives thereof (S–S Bidentates and S S Tetraden thraquinone; 1,8-dimercaptodithioanthraquinone; and beta tates) that meet the requirements for use as “wide band mercaptothiobenzophenone. 25 valence stabilizers for Mn" and/or Mn' include, but are not limited to: perthioacetic acid; perthiopropionic acid; per SValence Stabilizer #25: Examples of N-(aminomethylthiol) thiobenzoic acid; perthiophenylacetic acid; perthiocyclohex thioureas N-(aminomercaptomethyl)thioureas, bisN-(ami anoic acid; perthiofuroic acid; perthionaphtholic acid; phenyl nomethylthiol)thioureas, and polyN-(aminomethylthiol) perthioacetate; phenylperthiopropionate; phenylperthioben thioureas (S-S Bidentates, S S Tridentates, S. S 30 Zoate; phenyl perthiocyclohexanoate; phenyl perthiofuroate; Tetradentates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but phenyl perthionaphthoate; perthiooxalic acid; perthioma are not limited to: N'-(aminomercaptomethyl)thiourea; lonic acid; perthiosuccinic acid; diphenyl perthiooxalate: N,N'-dimethyl-N'-(aminomercaptomethyl)thiourea; N,N'- diphenyl perthiomalonate; diphenyl perthiosuccinate; dithi diethyl-N'-(aminomercaptomethyl)thiourea; N.N"-isopro ole-3-thione (dithione-3-thione); and benzodithiole-3-thione pyl-N'-(aminomercaptomethyl)thiourea; N,N'-diphenyl-N'- 35 (benzodithione-3-thione). (aminomercaptomethyl)thiourea; N,N'-dibenzyl-N'- S Valence Stabilizer #30: Examples of dithiocarbonates, (aminonercaptomethyl)thiourea; N,N'-dicyclohexyl-N'- trithiocarbonates, perthiocarbonates, bis(dithiocarbonates), (aminomercaptomethyl)thiourea; and N,N'-dinorbornyl-N'- bis (trithiocarbonates), and bis (perthiocarbonates) (S–S (aminomercaptomethyl)thiourea. Bidentates and S S Tetradentates) that meet the require 40 ments for use as “wide band” valence stabilizers for Mn' S Valence Stabilizer #26: Examples of dithiooxamides, bis and/or Mn' include, but are not limited to: S.S.-diethyldithio (dithiooxamides), and poly(dithiooxamides) (S-S Biden carbonate: S.S.-diisopropyldithiocarbonate: S.S.-diphe tates, S S Tridentates, S S Tetradentates) that meet the nyldithiocarbonate: S.S.-dibenzyldithiocarbonate: S.S.-dicy requirements for use as “wide band valence stabilizers for clohexyldithiocarbonate; S.S.-dinorbornyldithiocarbonate: Mn" and/or Mn" include, but are not limited to: dithiooxa 45 mide (rubeanic acid), N-methyldithiooxamide: N-eth diethyltrithiocarbonate; diisopropyltrithiocarbonate; diphe yldithiooxamide; N-isopropyldithiooxamide: N-phe nyltrithiocarbonate: dibenzyltrithiocarbonate; dicyclohexyl nyldithiooxamide: N-benzyldithiooxamide: trithiocarbonate; and dinorbornyltrithiocarbonate. N-cyclohexyldithiooxamide: N-norbornyldithiooxamide: SValence Stabilizer #31: Examples of dithiocarbamates, bis N,N'-dimethyldithiooxamide: N,N'-diethyldithiooxamide: 50 (dithiocarbamates), and poly(dithiocarbamates) (including N,N'-diisopropyldithiooxamide: N,N'-diphenyldithiooxam N-hydroxydithiocarbamates and N-mercaptodithiocarbam ide; N,N'-dibenzyldithiooxamide: N,N'-dicyclohexy ates) (S–S Bidentates, S S Tridentates, and S S Tet ldithiooxamide; and N,N'-dinorbornyldithiooxamide. radentates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but are not SValence Stabilizer #27: Examples of 1,1-dithiolates, bis(1, 55 limited to: dimethyldithiocarbamate (dmdtc); di(trifluo 1-dithiolates), and poly(1,1-dithiolates) (S. S. Bidentates rodimethyl)dithiocarbamate: diethyldithiocarbamate and S S Tetradentates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn" (dedtc); dipropyldithiocarbamate; diisopropyldithiocarbam include, but are not limited to: 1,1-dicyano-2,2-ethylene ate: dibutyldithiocarbamate; ditertbutyldithiocarbamate: dithiolate (i-mnt); 1,1-dicarboalkoxy-2.2-ethylene dithiolate dicyanamidodithiocarbamate; azidothioformates; diphe 60 nyldithiocarbamate; di(pentafluorophenyl)dithiocarbamate; (DED); 1,1-di(trifluoromethyl)-2.2-ethylene dithiolate; 1,1- dibenzyldithiocarbamate; dinaphthyldithiocarbamate; dicy di(pentafluorophenyl)-2.2-ethylene dithiolate: 1-pentameth clohexyldithiocarbamate; dinorbornyldithiocarbamate; ylene-2.2-ethylene dithiolate; and 1-nitroethylene dithiolate. diadamantyldithiocarbamate; pyrrolidinodithiocarbamate SValence Stabilizer #28: Examples of dithiomonocarboxylic (pyrdtc); piperidinodithiocarbamate (pipdtc); morpholin acids, tri- and tetrathiodicarboxylic Acids, bis(dithiomono 65 odithiocarbamate (mordtc); thiamorpholinodithiocarbamate; carboxylic acids), bis(tri- and tetrathiodicarboxylic acids), 3-pyrrolinodithiocarbamate: pyrrolodithiocarbamate; poly(dithiomonocarboxylic acids), poly(tri- and tetrathiodi oxazolodithiocarbamate; isoxazolodithiocarbamate; thiaz US 7,789,958 B2 109 110 olodithiocarbamate; isothiazolodithiocarbamate; Zylimidodicarbonic acid, O.O'-dicyclohexylimidodicarbonic indolodithiocarbamate; carbazolodithiocarbamate; pyrazoli acid, and O,O'-dinorbornylimidodicarbonic acid. nodithiocarbamate; imidazolinodithiocarbamate; pyra O Valence Stabilizer i5: Examples of imidodisulfamic acid, Zolodithiocarbamate; imidazolodithiocarbamate; inda imidodisulfuric acid, bis(imidodisulfamic acid), bis(imido Zolodithiocarbamate; and triazolodithiocarbamate. disulfuric acid), poly(imidodisulfamic acid), and poly(imido S Valence Stabilizer #32: Examples of dithiocarbazates disulfuric acid) and derivatives thereof (O-O Bidentates, (dithiocarbazides), bis(dithiocarbazates), and poly(dithiocar O—O Tridentates, O O Tetradentates) that meet the requirements for use as “wide band valence stabilizers for bazates) (S S Bidentates, S S Tridentates, and S S Tet Mn" and/or Mn" include, but are not limited to: imidodis radentates; or possibly N-S Bidentates, N S Tridentates, 10 ulfamic acid, imidodisulfuric acid, N-phenylimidodisulfamic and N S Tetradentates) that meet the requirements for use as acid, N-benzylimidodisulfamic acid, N-cyclohexylimidodis “wide band' valence stabilizers for Mn" and/or Mn" ulfamic acid, N-norbornylimidodisulfamic acid, N,N'-diphe include, but are not limited to: N,N'-dimethyldithiocarbazate: nylimidodisulfamic acid, N,N'-dibenzylimidodisulfamic N,N'-dictrifluoromethyl)dithiocarbazate: N,N'-diethyldithio acid, N,N'-dicyclohexylimidodisulfamic acid, and N,N'-nor carbazate; N.N'-diphenyldithiocarbazate; N.N'-diben 15 bornylimidodisulfamic acid. Zyldithiocarbazate; N.N'-dicpentafluorophenyl)dithiocarba Zate; N.N'-dicyclohexyldithiocarbazate; and N,N'- O Valence Stabilizer #6: Examples of 1,3-diketones (beta dinorbornyldithiocarbazate. diketonates), 1.3.5-triketones, bis(1,3-diketones), and poly (1,3-diketones), all with a molecular weight greater than 125 SValence Stabilizer #33: Examples of thiocyanate ligands (S (O-O Bidentates, O—O Tridentates, O—O Tetradentates) monodentates) that meet the requirements for use as “narrow that meet the requirements for use as “wide band valence band valence stabilizers for Mn" and/or Mn" include, but stabilizers for Mn" and/or Mn' include, but are not limited are not limited to: thiocyanate (—SCN). to: hexafluoropentanedione: dibenzoylmethane (1,3-diphe nyl-1,3-propanedione); benzoylpinacolone; dicyclohexoyl O Valence Stabilizer #1: Examples of biurets (imidodicar 25 methane; diphenylpentanetrionate; dibenzoylacetone; ben bonic diamides), isobiurets, bilureas, triurets, triureas, bis(bi Zoylacetylacetone; dibenzoylacetylacetone; urets), bis(isobiurets), bis(biureas), poly(biurets), poly(isobi tetramethylnonanetrionate; hexafluoroheptanetrionate; trif urets), and poly(biureas) (O-O Bidentates, O O Tridentates, O O Tetradentates) that meet the requirements luoroheptanetrionate; trifluoroacetylcamphor (facam); and for use as “wide band” valence stabilizers for Mn" and/or 1.3-indandione. Mn" include, but are not limited to:biuret, isobiuret, bilurea, 30 O Valence Stabilizer #7: Examples of 1,2-diketones (alpha triuret, triurea, nitrobiuret, dinitrobiuret, aminobiuret, diami diketonates), 1,2,3-triketones, tropolonates, o-quinones, bis nobiuret, oxybiuret, dioxybiuret, cyanobiuret, methylbiuret, (1,2-diketones), and poly(1,2-diketones), all with a molecular ethylbiuret, isopropylbiuret, phenylbiuret, benzylbiuret, weight greater than 100 (O-O Bidentates, O—O Triden cyclohexylbiuret, norbornylbiuret, adamantylbiuret, dimeth tates, O O Tetradentates) that meet the requirements for use ylbiuret, diethylbiuret, diisopropylbiuret, diphenylbiuret, 35 as “wide band' valence stabilizers for Mn" and/or Mn" dibenzylbiuret, dicyclohexylbiuret, dinorbornylbiuret, and include, but are not limited to: tropolone; 1,2-benzoquinone diadamantylbiuret. (o-quinone); di-tert-butyl-1,2-benzoquinone; hexafluoro-1, O Valence Stabilizer #2: Examples of acylureas, aroylureas, 2-benzoquinone; 1.2-naphthoduinone; 9,10-phenanthro bis(acylureas), bis(aroylureas), poly(acylureas), and poly 40 quinone; and 1.2-indandione. (aroylureas) (O-O Bidentates, O—O Tridentates, O O OValence Stabilizer #8: Examples of malonamides (malono Tetradentates) that meet the requirements for use as “wide diamides), bis(malonamides), and polymalonamides (O—O band valence stabilizers for Mn" and/or Mn" include, but Bidentates, O-O Tridentates, O O Tetradentates) that are not limited to: formylurea, acetylurea, benzoylurea, meet the requirements for use as “wide band valence stabi cyclohexoylurea, pentafluorobenzoylurea, N-methylacety 45 lizers for Mn" and/or Mn" include, but are not limited to: lurea, N-phenylbenzoylurea, and N-cyclohexylcyclohexoy malonamide, N-phenylmalonamide, N-benzylmalonamide, lurea. N-pentafluorophenylmalonamide, N-cyclohexylmalona O Valence Stabilizer #3: Examples of imidodialdehydes, mide, N-norbornylmalonamide, N,N'-diphenylmalonamide, hydrazidodialdehydes (acyl hydrazides), bis(imidodialde N,N'-dibenzylmalonamide, N,N'-dipentafluorophenylma hydes), bis(hydrazidodialdehydes), poly(imidodialdehydes), 50 lonamide, N,N'-dicyclohexylmalonamide, and N,N'-nor and poly(hydrazidodialdehydes) (O-O Bidentates, O O bornylmalonamide. Tridentates, O O Tetradentates) that meet the requirements O Valence Stabilizer #9: Examples of 2-acylacetamides, bis for use as “wide band valence stabilizers for Mn" and/or (2-acylacetamides), and poly(2-acylacetamides) (O—O Mn' include, but are not limited to: diacetamide, dipropana Bidentates, O-O Tridentates, O O Tetradentates) that mide, dibutanamide, dibenzamide, and dicyclohexamide. 55 meet the requirements for use as “wide band valence stabi lizers for Mn" and/or Mn" include, but are not limited to: OValence Stabilizer #4: Examples of imidodicarbonic acids, 2-acetoacetamide, N-phenyl-2-acetoacetamide, N-pen hydrazidodicarbonic acids, bis(imidodicarbonic acids), bis tafluorophenyl-2-acetoacetamide, N-benzyl-2-acetoaceta (hydrazidodicarbonic acids), poly(imidodicarbonic acids), mide, N-cyclohexyl-2-acetoacetamide, N-norbornyl-2-ac poly(hydrazidodicarbonic acids) and derivatives thereof 60 (O-O Bidentates, O—O Tridentates, O O Tetradentates) etoacetamide, N-phenyl-2-benzoacetamide, that meet the requirements for use as “wide band valence N-pentafluorophenyl-2-pentafluorobenzoacetamide, and stabilizers for Mn" and/or Mn" include, but are not limited N-cyclohexyl-2-cyclohexoacetamide. to: imidodicarbonic acid, hydrazidodicarbonic acid, O-phe O Valence Stabilizer #10: Examples of monothiodicarbonic nylimidodicarbonic acid, O-benzylimidodicarbonic acid, 65 diamides, bis(monothiodicarbonic diamides), and poly O-cyclohexylimidodicarbonic acid, O-norbornylimidodicar (monothiodicarbonic diamides) (O-O Bidentates, O O bonic acid, O.O'-diphenylimidodicarbonic acid, O.O'-diben Tridentates, O O Tetradentates) that meet the requirements US 7,789,958 B2 111 112 for use as “wide band” valence stabilizers for Mn" and/or O Valence Stabilizer #15: Examples of imidodiphosphoric Mn" include, but are not limited to: monothiodicarbonic acids, hydrazidodiphosphoric acids, bis(imidodiphosphoric diamide: N-phenylmonothiodicarbonic diamide: N-pen acids), bis(hydrazidodiphosphoric acids), poly(imidodiphos tafluorophenylmonothiodicarbonic diamide: N-benzylmono phoric acids), poly(hydrazidodiphosphoric acids), and thiodicarbonic diamide: N-cyclohexylmonothiodicarbonic derivatives thereof (O-O Bidentates, O-O Tridentates, diamide: N-norbornylmonothiodicarbonic diamide: N,N'- O—O Tetradentates) that meet the requirements for use as diphenylmonothiodicarbonic diamide; N.N'-dipentafluo “wide band valence stabilizers for Mn" and/or Mn" rophenylmonothiodicarbonic diamide: N,N'-dibenzylmono include, but are not limited to: imidodiphosphoric acid, meth thiodicarbonic diamide: N,N'- ylimidodiphosphoric acid, isopropylimidodiphosphoric acid, dicyclohexylmonothiodicarbonic diamide; and N,N'- 10 tert-butylimidodiphosphoric acid, phenylimidodiphosphoric dinorbornylmonothiodicarbonic diamide. acid, pentafluorophenylimidodiphosphoric acid, benzylimi O Valence Stabilizer #11: Examples of monothiodicarbonic dodiphosphoric acid, cyclohexylimidodiphosphoric acid, acids, bis(monothiodicarbonic acids), poly(monothiodicar norbornylimidodiphosphoric acid, dimethylimidodiphos bonic acids), and derivatives thereof (O-O Bidentates, phoric acid, diisopropylimidodiphosphoric acid, di-tert-bu O—O Tridentates, O O Tetradentates) that meet the 15 tylimidodiphosphoric acid, diphenylimidodiphosphoric acid, requirements for use as “wide band valence stabilizers for di-pentafluorophenylimidodiphosphoric acid, dibenzylimi Mn" and/or Mn' include, but are not limited to: mono dodiphosphoric acid, dicyclohexylimidodiphosphoric acid, thiodicarbonic acid, O-phenylmonothiodicarbonic acid, and dinorbornylimidodiphosphoric acid. O-benzylmonothiodicarbonic acid, O-cyclohexylmono thiodicarbonic acid, O-norbornylmonothiodicarbonic acid, O Valence Stabilizer #16: Examples of imidodiphosphora O.O'-diphenylmonothiodicarbonic acid, O.O'-dibenzyl mides, hydrazidodiphosphoramides, bis(imidodiphosphora monothiodicarbonic acid, O.O'-dicyclohexylmonothiodicar mides), bis(hydrazidodiphosphoramides), poly(imido bonic acid, and O,O'-dinorbornylmonothiodicarbonic acid. diphosphoramides), and poly(hydrazidodiphosphoramides) (O-O Bidentates, O—O Tridentates, O—O Tetradentates) O Valence Stabilizer #12: Examples of trithionic acid, bis 25 that meet the requirements for use as “wide band valence (trithionic acid), poly(trithionic acid), and derivatives thereof stabilizers for Mn" and/or Mn" include, but are not limited (O-O Bidentates, O—O Tridentates, O O Tetradentates) to: imidodiphosphoramide, N-methylimidodiphosphora that meet the requirements for use as “wide band valence mide, N-isopropylimidodiphosphoramide, N-tert-butylimi stabilizers for Mn' and/or Mn' include, but are not limited dodiphosphoramide, N-phenylimidodiphosphoramide, to: diphenyl trithionate, dipentafluorodiphenyl trithionate, 30 N-pentafluorophenylimidodiphosphoramide, N-benzylimi dicyclohexyl trithionate, and dinorbornyl trithionate. dodiphosphoramide, N-cyclohexylimidodiphosphoramide, N-norbornylimidodiphosphoramide, N.N"-dimethylimido O Valence Stabilizer #13: Examples of hypophosphoric diphosphoramide, N,N'-diisopropylimidodiphosphora acids, bis(hypophosphoric acids), and poly(hypophosphoric mide, N.N"-di-tert-butylimidodiphosphoramide, N.N"- acids), and derivatives thereof (O-O Bidentates, O-O Tri dentates, O O Tetradentates) that meet the requirements for 35 diphenylimidodiphosphoramide, N,N'-di use as “wide band valence stabilizers for Mn" and/or Mn" pentafluorophenylimidodiphosphoramide, N,N"- include, but are not limited to: hypophosphoric acid, O-me dibenzylimidodiphosphoramide, N,N"- thylhypophosphoric acid, O-isopropylhypophosphoric acid, dicyclohexylimidodiphosphoramide, and N,N"- O-tert-butylhypophosphoric acid, O-phenylhypophosphoric dinorbornylimidodiphosphoramide. acid, O-pentafluorophenylhypophosphoric acid, O-benzyl 40 O Valence Stabilizer #17: Examples of diphosphoramides, hypophosphoric acid, O-cyclohexylhypophosphoric acid, bis(diphosphoramides), and poly(diphosphoramides) (O—O O-norbornylhypophosphoric acid, O.O"-dimethylhypophos Bidentates, O-O Tridentates, O O Tetradentates) that phoric acid, O.O"-diisopropylhypophosphoric acid, O,O'-di meet the requirements for use as “wide band valence stabi tert-butylhypophosphoric acid, O.O"-diphenylhypophospho lizers for Mn" and/or Mn" include, but are not limited to: ric acid, O.O'-di-pentafluorophenylhypophosphoric acid, 45 diphosphoramide, N-methyldiphosphoramide, N-isopropyl O.O"-dibenzylhypophosphoric acid, O.O"-dicyclohexylhy diphosphoramide, N-tert-butyldiphosphoramide, N-phenyl pophosphoric acid, and O.O"-dinorbornylhypophosphoric diphosphoramide, N-pentafluorophenyldiphosphoramide, acid. N-benzyldiphosphoramide, N-cyclohexyldiphosphoramide, N-norbornyldiphosphoramide, N.N"-dimethyldiphosphora OValence Stabilizer #14: Examples of hypophosphoramides, 50 mide, N.N"-diisopropyldiphosphoramide, N.N"-di-tert-bu bis(hypophosphoramides), and poly(hypophosphoramides) tyldiphosphoramide, N.N"-diphenyldiphosphoramide, (O-O Bidentates, O—O Tridentates, O O Tetradentates) N,N'-di-pentafluorophenyldiphosphoramide, N.N"-diben that meet the requirements for use as “wide band valence Zyldiphosphoramide, N.N"-dicyclohexyldiphosphoramide, stabilizers for Mn" and/or Mn" include, but are not limited and N.N"-dinorbornyldiphosphoramide. to: hypophosphoramide, N-methylhypophosphoramide, 55 N-isopropylhypophosphoramide, N-tert-butylhypophos OValence Stabilizer #18: Examples of beta-hydroxyketones, phoramide, N-phenylhypophosphoramide, N-pentafluo beta-hydroxyaldehydes, bis(beta-hydroxyketones), bis(beta rophenylhypophosphoramide, N-benzylhypophosphora hydroxyaldehydes), poly(beta-hydroxyketones), and poly mide, N-cyclohexylhypophosphoramide, (beta-hydroxyaldehydes) (O-O Bidentates, O—O Triden N-norbornylhypophosphoramide, N.N"-dimethylhypophos 60 tates, O O Tetradentates) that meet the requirements for use phoramide, N.N"-diisopropylhypophosphoramide, N.N"- as “wide band' valence stabilizers for Mn" and/or Mn" di-tert-butylhypophosphoramide, N.N"-diphenylhypophos include, but are not limited to: 4-hydroxypentan-2-one; 1,3- phoramide, N,N'-di diphenyl-3-hydroxypropanal; 1,3-dibenzyl-3-hydroxypro pentafluorophenylhypophosphoramide, N,N'- panal; 1,3-dicyclohexyl-3-hydroxypropanal; 1,3-dinor dibenzylhypophosphoramide, N,N"- 65 bornyl-3-hydroxypropanal; 1,3-di(2-thienyl)-3- dicyclohexylhypophosphoramide, and N,N"- hydroxypropanal; 1,3-di(2-furyl)-3-hydroxypropanal; dinorbornylhypophosphoramide. o-hydroxyacetophenone; juglone; allizarin; 1-hydroxyan US 7,789,958 B2 113 114 thraquinone; 1.8-hydroxyanthraquinone; 1-hydroxyacri isopropylcarbimate; butylcarbimate; tertbutylcarbimate: done; and beta-hydroxybenzophenone. cyanocarbimate; cyanamidocarbimate; azidocarbimate; phe O Valence Stabilizer #19. Examples of N-(aminomethylol) nylcarbimate; pentafluorophenylcarbimate; benzylcarbi ureas N-(aminohydroxymethyl)ureas, bisN-(aminomethy mate; naphthylcarbimate; cyclohexylcarbimate; norbornyl lol)ureas, and polyN-(aminomethylol)ureas(O-O Biden carbimate; and adamantylcarbimate. Note: Carbimates tend tates, O O Tridentates, O O Tetradentates) that meet the to stabilize lower oxidation states in metal ions. requirements for use as “wide band valence stabilizers for O Valence Stabilizer #25. Examples of cyanate ligands (O Mn" and/or Mn" include, but are not limited to: N'-(amino hydroxymethyl)urea; N,N'-dimethyl-N'-(aminohydroxym monodentates) that meet the requirements for use as “wide ethyl)urea; N,N'-diethyl-N'-(aminohydroxymethyl)urea; 10 band valence stabilizers for Mn" and/or Mn" include, but N,N'-isopropyl-N'-(aminohydroxymethyl)urea; N,N'- are not limited to: cyanate ( OCN). diphenyl-N'-(aminohydroxymethyl)urea; N,N'-dibenzyl-N'- N SValence Stabilizer #1: Examples of diformamidine dis (aminohydroxymethyl)urea; N,N'-dicyclohexyl-N'-(amino ulfides (thioperoxydicarbonimidic diamides), thioperoxytri hydroxymethyl)urea; and N,N'-dinorbornyl-N'- carbonimidic diamides, thioperoxytetracarbonimidic dia (aminohydroxymethyl)urea. 15 mides, bis(diformamidine disulfides), and poly (diformamidine disulfides) (N–S bidentates, N N S O Valence Stabilizer #20: Examples of oxamides, bis(oxam tridentates, or N-S tetradentates) that meet the requirements ides), and poly(oxamides) (O-O Bidentates, O O Triden for use as “wide band valence stabilizers for Mn" and/or tates, O O Tetradentates) that meet the requirements for use Mn' include, but are not limited to: diformamidine disulfide; as “wide band valence stabilizers for Mn" and/or Mn" methyldiformamidine disulfide; ethyldiformamidine disul include, but are not limited to: oxamide, N-methyloxamide: fide: isopropyldiformamidine disulfide; butyldiformamidine N-ethyloxamide: N-isopropyloxamide: N-phenyloxamide: disulfide; benzyldiformamidine disulfide: phenyldiformami N-benzyloxamide: N-cyclohexyloxamide: N-norbornyloxa dine disulfide; tolyldiformamidine disulfide; naphthyldifor mide: N,N'-dimethyloxamide: N,N'-diethyloxamide: N,N'- mamidine disulfide; cyclohexyldiformamidine disulfide; nor diisopropyloxamide: N,N'-diphenyloxamide: N,N'-dibenzy 25 bornyldiformamidine disulfide; adamantyldiformamidine loxamide; N,N'-dicyclohexyloxamide: and N,N'- disulfide; dimethyldiformamidine disulfide; diethyldiforma dinorbornyloxamide. midine disulfide; diisopropyldiformamidine disulfide: dibu O Valence Stabilizer #21: Examples of squaric acids and tyldiformamidine disulfide: dibenzyldiformamidine disul derivatives thereof (O-O Bidentates) that meet the require fide:diphenyldiformamidine disulfide; ditolyldiformamidine ments for use as “wide band valence stabilizers for Mn" 30 disulfide; dinaphthyldiformamidine disulfide; dicyclohexy and/or Mn' include, but are not limited to: deltic acid: ldiformamidine disulfide; dinorbornyldiformamidine disul squaric acid; croconic acid; and rhodizonic acid. fide: diadamantyldiformamidine disulfide: 2-S-amidinodis ulfidothiazole; 2-S-amidinodisulfidooxazole; 2-S- O Valence Stabilizer #22: Examples of dicarboxylic acids, amidinodisulfidoimidazole; 3-S-amidinodisulfidopyrazole; bis(dicarboxylic acids), poly(dicarboxylic acids), and deriva 35 tives thereof (O-O Bidentates and O—O Tetradentates) that 3-S-amidinodisulfido-1,2,4-triazole; and 5-S-amidinodisul meet the requirements for use as “wide band valence stabi fidotetrazole. lizers for Mn" and/or Mn" include, but are not limited to: N—S Valence Stabilizer #2: Examples of S-amidinodithio oxalic acid; malonic acid; Succinic acid; diphenyl oxalate; carbamates, bis(S-amidinodithiocarbamates), and poly(S- diphenyl malonate; and diphenyl Succinate. 40 amidinodithiocarbamates) (N. S. Bidentates and N S Tet radentates) that meet the requirements for use as “wide band O Valence Stabilizer #23: Examples of carbamates, bis(car valence stabilizers for Mn" and/or Mn" include, but are not bamates), and poly(carbamates) (including N-hydroxycar limited to: S-amidinodithiocarbamate; N-methyl-S-amidin bamates and N-mercaptocarbamates) (O-O Bidentates, odithiocarbamate; N-ethyl-S-amidinodithiocarbamate: O—O Tridentates, and O—O Tetradentates) that meet the 45 N-isopropyl-S-amidinodithiocarbamate; N-butyl-S-amidin requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but are not limited to: dimethyl odithiocarbamate; N-benzyl-S-amidinodithiocarbamate: carbamate (dmc); di(trifluorodimethyl)carbamate; ethyl car N-phenyl-S-amidinodithiocarbamate; N-tolyl-S-amidin bamate; diethylcarbamate (dec); dipropylcarbamate; diiso odithiocarbamate; N-naphthyl-S-amidinodithiocarbamate: propylcarbamate: dibutylcarbamate; ditertbutylcarbamate; N-cyclohexyl-S-amidinodithiocarbamate; N-norbornyl-S- dicyanamidocarbamate; diphenylcarbamate; di(pentafluo 50 amidinodithiocarbamate; N-adamantyl-S-amidinodithiocar rophenyl)carbamate: dibenzylcarbamate; dinaphthylcarbam bamate; N.N'-dimethyl-S-amidinodithiocarbamate: N,N'-di ate; dicyclohexylcarbamate; dinorbornylcarbamate; diada ethyl-S-amidinodithiocarbamate: N,N'-diisopropyl-S- mantylcarbamate; pyrrolidinocarbamate (pyrc); amidinodithiocarbamate; N,N'-dibutyl-S- piperidinocarbamate (pipc); morpholinocarbamate (morc); amidinodithiocarbamate; N,N'-dibenzyl-S- thiamorpholinocarbamate; 3-pyrrolinocarbamate; pyrrolo 55 amidinodithiocarbamate; N,N'-diphenyl-S- carbamate; oxazolocarbamate; isoxazolocarbamate; thiaz amidinodithiocarbamate; N,N'-ditolyl-S- olocarbamate; isothiazolocarbamate; indolocarbamate; car amidinodithiocarbamate; N,N'-dinaphthyl-S- baZolocarbamate; pyrazolinocarbamate; amidinodithiocarbamate; N,N'-dicyclohexyl-S- imidazolinocarbamate; pyrazolocarbamate; imidazolocar amidinodithiocarbamate; N,N'-dinorbornyl-S- 60 amidinodithiocarbamate; N,N'-diadamantyl-S- bamate; indaZolocarbamate; and triazolocarbamate. amidinodithiocarbamate; ethylenebis(S- OValence Stabilizer #24: Examples of carbimates, bis(carbi amidinodithiocarbamate); propylenebis(S- mates), and poly(carbimates) (O-O Bidentates, O O Tri amidinodithiocarbamate); phenylenebis(S- dentates, and O-O Tetradentates) that meet the requirements amidinodithiocarbamate); piperazinebis(S- for use as “wide band” valence stabilizers for Mn" and/or 65 amidinodithiocarbamate); oxalylbis(S- Mn" include, but are not limited to: methylcarbimate; trif amidinodithiocarbamate); malonylbis(S- luoromethylcarbimate; ethylcarbimate; propylcarbimate; amidinodithiocarbamate); succinylbis(S- US 7,789,958 B2 115 116 amidinodithiocarbamate); phthalylbis(S- amidinoperoxythiocarbamate); propylenebis(S-amidinoper amidinodithiocarbamate); 2-S-dithiocarbamatothiazole; oxythiocarbamate); phenylenebis(S-amidinoperoxythiocar 2-S-dithiocarbamatooxazole; 2-S-dithiocarbamatoimida bamate); piperazinebis(S-amidinoperoxythiocarbamate); Zole: 3-S-dithiocarbamatopyrazole; 3-S-dithiocarbamato-1, oxalylbis (S-amidinoperoxythiocarbamate); malonylbis 2,4-triazole; and 5-S-dithiocarbamatotetrazole. (S-amidinoperoxythiocarbamate); Succinylbis(S-amidinop eroxythiocarbamate); and phthalylbis(S-amidinoperoxythio N—SValence Stabilizer #3: Examples of O-amidinothiocar bamates, bis(O-amidinothiocarbamates), and poly(O-amidi carbamate). nothiocarbamates) (N. S. Bidentates and N S Tetraden N—S Valence Stabilizer #5. Examples of phosphorimidot tates) that meet the requirements for use as “wide band hioic acid; phosphorimidodithioic acid; phosphorimidot valence stabilizers for Mn" and/or Mn' include, but are not 10 rithioic acid; bis(phosphorimidothioic acid); bis(phospho limited to: O-amidinothiocarbamate; N-methyl-O-amidi rimidodithioic acid); bis(phosphorimidotrithioic acid); poly nothiocarbamate; N-ethyl-O-amidinothiocarbamate; N-iso (phosphorimidothioic acid); poly(phosphorimidodithioic propyl-O-amidinothiocarbamate; N-butyl-O-amidinothio acid); poly(phosphorimidotrithioic acid); and derivatives carbamate; N-benzyl-O-amidinothiocarbamate; N-phenyl thereof (N. S. Bidentates and N S Tetradentates) that meet O-amidinothiocarbamate; N-tolyl-O-amidinothiocarbamate: 15 the requirements for use as “wide band valence stabilizers N-naphthyl-O-amidinothiocarbamate; N-cyclohexyl-O-ami for Mn" and/or Mn" include, but are not limited to: phos dinothiocarbamate; N-norbornyl-O-amidinothiocarbamate: phorimidothioic acid; phosphorimidodithioic acid; phospho N-adamantyl-O-amidinothiocarbamate: N,N'-dimethyl-O- rimidotrithioic acid; O-phenylphosphorimidothioic acid; amidinothiocarbamate; N.N'-diethyl-O-amidinothiocarbam O-benzylphosphorimidothioic acid; O-cyclohexylphospho ate; N.N'-diisopropyl-O-amidinothiocarbamate; N.N'-dibu rimidothioic acid; O-norbornylphosphorimidothioic acid; tyl-O-amidinothiocarbamate; N,N'-dibenzyl-O- O.O'-diphenylphosphorimidothioic acid; O,O'-diben amidinothiocarbamate; N,N'-diphenyl-O- Zylphosphorimidothioic acid; O,O'-dicyclohexylphospho amidinothiocarbamate; N,N'-ditolyl-O- rimidothioic acid; and O,O'-dinorbornylphosphorimidot amidinothiocarbamate; N,N'-dinaphthyl-O- hioic acid. amidinothiocarbamate; N,N'-dicyclohexyl-O- 25 amidinothiocarbamate; N,N'-dinorbornyl-O- N—S Valence Stabilizer #6: Examples of phosphorothioic amidinothiocarbamate; N,N'-diadamantyl-O- triamides, bis(phosphorothioic triamides), and poly(phos amidinothiocarbamate; ethylenebis(O- phorothioic triamides) (N. S. Bidentates and N S Tetraden amidinothiocarbamate); propylenebis(O- tates) that meet the requirements for use as “wide band 30 valence stabilizers for Mn" and/or Mn" include, but are not amidinothiocarbamate); phenylenebis(O- limited to: phosphorothioic triamide: phosphorothioic trihy amidinothiocarbamate); piperazinebis(O- drazide: phosphoramidothioic dihydrazide: N-phenylphos amidinothiocarbamate); oxalylbis(O- phorothioic triamide: N-benzylphosphorothioic triamide: amidinothiocarbamate); malonylbis(O- N-cyclohexylphosphorothioic triamide: N-norbornylphos amidinothiocarbamate); succinylbis(O- 35 phorothioic triamide: N,N'-diphenylphosphorothioic tria amidinothiocarbamate); phthalylbis(O- mide: N,N'-dibenzylphosphorothioic triamide: N,N'-dicyclo amidinothiocarbamate): 2-O-monothiocarbamatothiazole; 2-O-monothiocarbamatooxazole: 2-O-monothiocarbama hexylphosphorothioic triamide; and N,N'- toimidazole: 3-O-monothiocarbamatopyrazole: 3-O-mono dinorbornylphosphorothioic triamide. thiocarbamato-1,2,4-triazole; and 5-O-monothiocarbama N—S Valence Stabilizer #7: Examples of phosphoramidot totetrazole. 40 rithioic acid, phosphorodiamidodithioic acid, bis(phosphora N—S Valence Stabilizer #4: Examples of S-amidinoperox midotrithioic acid), bis(phosphorodiamidodithioic acid), ythiocarbamates, bis(S-amidinoperoxythiocarbamates), and poly(phosphoramidotrithioic acid), poly(phosphorodiami dodithioic acid), and derivatives thereof (N. S. Bidentates poly(S-amidinoperoxythiocarbamates) (N. S. Bidentates and N S Tetradentates) that meet the requirements for use as and N S Tetradentates) that meet the requirements for use as 45 “wide band valence stabilizers for Mn" and/or Mn" “wide band valence stabilizers for Mn" and/or Mn" include, but are not limited to: phosphoramidotrithioic acid, include, but are not limited to: S-amidinoperoxythiocarbam phosphorodiamidodithioic acid, S-phenylphosphoramidot ate; N-methyl-S-amidinoperoxythiocarbamate; N-ethyl-S- rithioic acid, S-benzylphosphoramidotrithioic acid, S-cyclo amidinoperoxythiocarbamate; N-isopropyl-S-amidinoper hexylphosphoramidotrithioic acid, S-norbornylphosphora oxythiocarbamate, N-butyl-S-amidinoperoxythiocarbamate: 50 N-benzyl-S-amidinoperoxythiocarbamate; N-phenyl-S-ami midotrithioic acid, S.S'-diphenylphosphoramidotrithioic dinoperoxythiocarbamate; N-tolyl-S-amidinoperoxythiocar acid, S.S'-dibenzylphosphoramidotrithioic acid, S.S'-dicy bamate; N-naphthyl-S-amidinoperoxythiocarbamate. N-cy clohexylphosphoramidotrithioic acid, and S.S'-dinor clohexyl-S-amidinoperoxythiocarbamate; N-norbornyl-S- bornylphosphoramidotrithioic acid. amidinoperoxythiocarbamate; N-adamantyl-S- 55 N—S Valence Stabilizer #8: Examples of phosphoramidot amidinoperoxythiocarbamate; N,N'-dimethyl-S- hioic acid, phosphoramidodithioic acid, phosphorodiamidot amidinoperoxythiocarbamate; N,N'-diethyl-S- hioic acid, bis(phosphoramidothioic acid), bis(phosphorami amidinoperoxythiocarbamate; N,N'-diisopropyl-S- dodithioic acid), bis(phosphorodiamidothioic acid), poly amidinoperoxythiocarbamate; N,N'-dibutyl-S- (phosphoramidothioic acid), poly(phosphoramidodithioic amidinoperoxythiocarbamate; N,N'-dibenzyl-S- 60 acid), and poly(phosphorodiamidothioic acid) (N–S Biden amidinoperoxythiocarbamate; N,N'-diphenyl-S- tates and N S Tetradentates) that meet the requirements for amidinoperoxythiocarbamate; N,N'-ditolyl-S- use as “wide band valence stabilizers for Mn" and/or Mn" amidinoperoxythiocarbamate; N,N'-dinaphthyl-S- include, but are not limited to: phosphoramidothioic acid, amidinoperoxythiocarbamate; N,N'-dicyclohexyl-S- phosphoramidodithioic acid, phosphorodiamidothioic acid, amidinoperoxythiocarbamate; N,N'-dinorbornyl-S- 65 phosphorohydrazidothioic acid, phosphorohydrazidodithioic amidinoperoxythiocarbamate; N,N'-diadamantyl-S- acid, phosphorodihydrazidothioic acid, phosphoramidohy amidinoperoxythiocarbamate; ethylenebis(S- drazidothioic acid, O-phenylphosphoramidothioic acid, US 7,789,958 B2 117 118 O-benzylphosphoramidothioic acid, O-cyclohexylphos phthalimide dithiosemicarbazone; furaldehyde thiosemicar phoramidothioic acid, O-norbornylphosphoramidothioic baZone; naphthoguinone thiosemicarbazone; phenanthre acid, S-phenylphosphoramidodithioic acid, S-benzylphos quinone thiosemicarbazone; cyclohexanedione dithiosemi phoramidodithioic acid, S-cyclohexylphosphorami carbazone; iononethiosemicarbazone; bisthiosemicarbazone dodithioic acid, and S-norbornylphosphoramidodithioic of diethyl-3,4-dioxadioate; pyridoxal alkylthiosemicarba acid. Zones; benzylidene phenylthiosemicarbazones; lawsone thi N—S Valence Stabilizer #9: Examples of N-thioacyl 7-ami osemicarbazone; and 1-benzoin-4-phenylthiosemicarbazone nobenzylidenimines (N-S Bidentates or N-S Tetraden (bps). tates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn' include, but are not 10 N—S Valence Stabilizer #13: Examples of thioacyl hydra limited to: N-thioacetyl 7-methylaminobenzylidenimine: Zones, bis(thioacyl hydrazones), and poly(thioacyl hydra N-thioacetyl 7-phenylaminobenzylidenimine; N-thioben Zones) (N–S Bidentates, N S Tetradentates, and N—S Zoyl 7-methylaminobenzylidenimine; and N-thiobenzoyl Hexadentates) that meet the requirements for use as “wide 7-phenylaminobenzylidenimine. band' valence stabilizers for Mn, and/or Mn" include, but 15 are not limited to: acetaldehyde N-thioformylhydrazone: N—SValence Stabilizer #10: Examples of thiohydroxamates acetaldehyde N-thiobenzoylhydrazone; acetone N-thio (thiohydroxylamines), bis(thiohydroxamates), and poly formylhydrazone; acetone N-thiobenzoylhydrazone; pina (thiohydroxamates) (N–S Bidentates, N S Tetradentates, colone N-thioformylhydrazone; pinacolone N-thiobenzoyl and N S Hexadentates) that meet the requirements for use as hydrazone; benzaldehyde N-thioformylhydrazone: “wide band valence stabilizers for Mn" and/or Mn" benzaldehyde N-thiobenzoylhydrazone; naphthaldehyde include, but are not limited to: acetothiohydroxamic acid; propianothiohydroxamic acid; butyrothiohydroxamic acid; N-thioformylhydrazone; naphthaldehyde N-thiobenzoylhy crotonothiohydroxamic acid; Sorbothiohydroxamic acid; drazone; norbornanone N-thioformylhydrazone; norbor benzothiohydroxamic acid; toluicthiohydroxamic acid; sali nanone N-thiobenzoylhydrazone; camphor N-thioformylhy cylthiohydroxamic acid; phenylacetothiohydroxamic acid; 25 draZone; camphor N-thiobenzoylhydrazone; nopinone anthranilthiohydroxamic acid; nicotinethiohydroxamic acid; N-thioformylhydrazone; nopinone N-thiobenzoylhydrazone: picolinethiohydroxamic acid; cyclohexanethiohydroxamic 2-pyridinaldehyde N-thioformylhydrazone: 2-pyridinalde acid; quinoline 8-thiohydroxamic acid; cinnamylthiohydrox hyde N-thiobenzoylhydrazone; salicylaldehyde N-thio amic acid, oxaldithiohydroxamic acid; Succinylbis-N-phe formylhydrazone; salicylaldehyde N-thiobenzoylhydrazone: nylthiohydroxamic acid; adipylbis-N-phenylthiohydroxamic 30 quinolinaldehyde N-thioformylhydrazone; quinolinaldehyde acid; glyoxalthiohydroxamic acid; 2-thiophenethiocarbohy N-thiobenzoylhydrazone; thiophene-2-aldehyde N-thio droxamic acid; thenoylthiohydroxamic acid; N-phenylben formylhydrazone; thiophene-2-aldehyde N-thiobenzoylhy Zothiohydroxamic acid; N-tolylbenzothiohydroxamic acid; draZone; naphthoquinone N-thioformylhydraZone; naphtho N-phenylacetothiohydroxamic acid; N-phenyl-2-thenoylth quinone N-thiobenzoylhydrazone: ionone iohydroxamic acid; and N-tolyl-2-thenoylthiohydroxamic 35 N-thioformylhydrazone; ionone N-thiobenzoylhydrazone: acid. benzaldehyde benzothiazolehydrazone: lawsone N-thio N—S Valence Stabilizer #11: Examples of alpha- or ortho formylhydrazone; and lawsone N-thiobenzoylhydrazone. aminothiocarboxylic acids, and alpha- or ortho-aminothiodi N—S Valence Stabilizer #14: Examples of thiocarbazones carboxylic acids, and derivatives thereof (N-S Bidentates, 40 (diaZenecarbothioic hydrazides), bis(thiocarbazones), and N—S Tridentates, and N S Tetradentates) that meet the poly(thiocarbazones) (N–S Bidentates, N S Tetradentates, requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but are not limited to: 2-pyridi and N S Hexadentates) that meet the requirements for use as nethiocarboxylic acid (thiopicolinic acid); 2-pyrazinethio “wide band valence stabilizers for Mn" and/or Mn" carboxylic acid; o-aminothiobenzoic acid; o-aminothionaph include, but are not limited to: diphenylthiocarbazone (di 45 thizone); 2-phenylthiocarbazone; dinaphthylthiocarbazone; thoic acid; and 3,6-diaminothiophthalic acid. 2-naphthylthiocarbazone; and ambazone. N—S Valence Stabilizer #12: Examples of thiosemicarba N—S Valence Stabilizer #15: Examples of azo compounds Zones, bis(thiosemicarbazones), and poly(thiosemicarba with thiol or mercapto or thiocarbonyl substitution at the Zones) (N–S Bidentates, N S Tetradentates, and N—S ortho- (for aryl) or alpha- or beta- (for alkyl) positions, Bis Hexadentates) that meet the requirements for use as “wide 50 o-(HS ) or alpha- or beta-(HS-)azo compounds, or Poly band valence stabilizers for Mn" and/or Mn" include, but o-(HS ) or alpha- or beta-(HS-)azo compounds) (N–S are not limited to: acetaldehyde thiosemicarbazone; acetone Bidentates, N–S Tridentates, N S Tetradentates, or N–S thiosemicarbazone; pinacolone thiosemicarbazone; benzal Hexadentates) that meet the requirements for use as “wide dehyde thiosemicarbazone; naphthaldehyde thiosemicarba band valence stabilizers for Mn" and/or Mn" include, but Zone; norbornanone thiosemicarbazone; camphor thiosemi 55 are not limited to: 2-thiolazobenzene 1-(phenylazo)-2- carbazone; nopinone thiosemicarbazone; 2-pyridinaldehyde thiophenol; 2.2'-dithioazobenzene: (2-thiophene)azoben thiosemicarbazone; salicylaldehyde thiosemicarbazone; Zene: 1-(4-nitrophenylazo)-2-thionaphthol; 2-thiazolyla quinolinaldehyde thiosemicarbazone; isatin dithiosemicar baZone; camphorquinone dithiosemicarbazone; cam Zobenzene; and 2-benzothiazolylazobenzene. phorquinone dithiosemicarbazone; picolinaldehyde thi 60 N—S Valence Stabilizer #16: Examples of diazenefor osemicarbazone; dipyridyl glyoxal dithiosemicarbazone; mothioamides, diaZeneacetothioamides, bis(diaZenefor di-2-pyridyl ketone thiosemicarbazone; methyl-2-pyridyl mothioamides), bis(diaZeneacetothioamides), poly(diazene ketone thiosemicarbazone; glyoxal dithiosemicarbazone; formothioamides), and poly(diazeneacetothioamides) (N–S acetophenone thiosemicarbazone; biacetyl monoxime thi Bidentates, N S Tetradentates, and N—S Hexadentates) osemicarbazone; acetamidobenzaldehyde thiosemicarba 65 that meet the requirements for use as “wide band valence Zone; thymolaldothiosemicarbazone; thiophene-2-aldehyde stabilizers for Mn" and/or Mn" include, but are not limited thiosemicarbazone: phthalaldehyde dithiosemicarbazone: to: diaZeneformothioamide, diaZeneacetothioamide, phenyl US 7,789,958 B2 119 120 diaZeneformothioamide, diphenyldiaZeneformothioamide, and/or Mn" include, but are not limited to: 1-(2-thiophenyl)- phenyldiazeneacetothioamide, and diphenyldiazeneac 3,5-diphenylformazan: 1-(2-methylmercaptophenyl)-3,5- etothioamide. diphenylformazan; 1.5-bis(2-thiophenyl)-3-phenylforma Zan, and 5-bis(2-methylmercaptophenyl)-3- N—S Valence Stabilizer #17: Examples of diaZenecarboth phenylformazan. ioic acids, diaZenecarbodithioic acids, bis(diaZenecarboth ioic acids), bis(diazenecarbodithioic acids), poly(diaZenecar N—S Valence Stabilizer #23: Examples of ortho-thio (or bothioic acids), poly(diazenecarbodithioic acids) and -mercapto) Substituted azines (including ketazines), bis(o- derivatives thereof (N. S. Bidentates, N S Tetradentates, thio or mercapto Substituted azines), and poly(o-thio or mer N—S Hexadentates) that meet the requirements for use as capto substituted azines) (N. S. Bidentates, N S Triden “wide band valence stabilizers for Mn" and/or Mn" 10 tates, N—S Tetradentates, and N S Hexadentates) that meet include, but are not limited to: diazeneformothioic acid, dia the requirements for use as “wide band valence stabilizers Zeneacetothioic acid, phenyldiazeneformothioic acid, diphe for Mn' and/or Mn' include, but are not limited to: 2-mer nyldiazeneformothioic acid, phenyldiazeneacetothioic acid, capto-1-benzalazine, 2-mercapto-1-naphthalazine; and and diphenyldiazeneacetothioic acid. 2-mercapto-1-cyclohexanonazine. 15 N—S Valence Stabilizer #18: Examples of diazenefor N–S Valence Stabilizer #24: Examples of Schiff Bases with mothioaldehydes, diaZeneacetothioaldehydes, bis(diazene one Imine (C—N) Group and with ortho- or alpha- or beta formothioaldehydes), bis(diazeneacetothioaldehydes), poly thio or mercapto or thiocarbonyl substitution (N–S Biden (diazeneformothioaldehydes), and poly tates, N–S Tridentates, N S Tetradentates, N–S Penta (diazeneacetothioaldehydes) (N–S Bidentates, N—S dentates, or N S Hexadentates) that meet the requirements Tetradentates and N S Hexadentates) that meet the require for use as “wide band valence stabilizers for Mn" and/or ments for use as “wide band” valence stabilizers for Mn' Mn' include, but are not limited to: N-(Thiosalicylaldehydo) and/or Mn" include, but are not limited to: diazenefor isopropylamine, N-(2-thiophenecarboxaldehydo)isopropy mothioaldehyde, diaZeneacetothioaldehyde, phenyldiazene lamine; N-(2-Acetylthiopheno)isopropylamine; N-(2-Thio formothioaldehyde, diphenyldiazeneformothioaldehyde, 25 acetophenono)isopropylamine; N-(Thiosalicylaldehydo) phenyldiazeneacetothioaldehyde, and diphenyldiazeneac cyclohexylamine; N-(2-Thiophenecarboxaldehydo) etothioaldehyde. cyclohexylamine, N-(2-Acetylthiopheno)cyclohexylamine; N-(2-Thioacetophenono)cyclohexylamine; N-(Thiosalicyla N—S Valence Stabilizer #19. Examples of diazenedifor ldehydo)aniline; N-(2-Thiophenecarboxaldehydo)aniline: mothioamides, diaZenediacetothioamides, bis(diaZenedifor 30 N-(2-Acetylthiopheno)aniline; N-(2-Thioacetophenono) mothioamides), bis(diazenediacetothioamides), poly(diaz aniline; N-(Thiosalicylaldehydo)aminonorbornane; N-(2- enediformothioamides), and poly Thiocarboxaldehydo)aminonorborname: N-(2-Acetylth (diazenediacetothioamides) (N S Tridentates and N—S iopheno)aminonorbornane; N-(2-Thioacetophenono) Hexadentates) that meet the requirements for use as “wide aminonorbornane; 4-aminobenzylidene-3-propyl-5- band valence stabilizers for Mn" and/or Mn" include, but 35 mercapto-1,2,4-triazole, 4-aminocinnamalidene-3-propyl-5- are not limited to: diaZenediformodithioamide, diaZenediac mercapto-1,2,4-triazole (acpmt), 4-aminosalicylidene-3- etodithioamide, diphenydiazenediformodithioamide, tet propyl-5-mercapto-1,2,4-triazole (aspmt); raphenyldiaZenediformodithioamide, diphenyldiazenediac 4-aminovanillidene-3-propyl-5-mercapto-1,2,4-triazole; etodithioamide, and tetraphenyldiaZenediacetodithioamide. 4-aminodimethylaminobenzylidene-3-propyl-5-mercapto-1, N—SValence Stabilizer #20. Examples of diazenedicarboth 40 2,4-triazole (adpmt); cinnamylideneaminophenylthiazole; ioic acids, diaZenedicarbodithioic acids, bis(diaZenedicar N-(2-mercaptophenyl)salicylidenimine; 2-thiophenecarbox bothioic acids), bis(diaZenedicarbodithioic acids), poly(dia aldehyde phenylhydrazone: 2-thiophenecarboxaldehyde Zenedicarbothioic acids), poly(diaZenedicarbodithioic acids) 2-pyridyl hydraZone: 2-mercaptobenzaldehyde phenylhydra and derivatives thereof (N S Tridentates and N S Hexa Zone; and 2-mercaptobenzaldehyde 2-pyridyl hydrazone. dentates) that meet the requirements for use as “wide band' 45 Also includes Schiff Bases derived from the reaction of car valence stabilizers for Mn" and/or Mn' include, but are not bonyl compounds with dithiocarbazates, and hydrazones limited to: diazenediformothioic acid, diazenediacetodithioic with ortho-S substitution. acid, phenyldiazenediformothioic acid, diphenyldiaZenedi N–S Valence Stabilizer #25: Examples of Schiff Bases formothioic acid, phenyldiaZenediacetodithioic acid, and with two Imine (C—N) Groups and with ortho- or alpha- or diphenyldiaZenediacetodithioic acid. 50 beta-thio or mercapto or thiocarbonyl substitution (N STri N—S Valence Stabilizer #21: Examples of diazenedifor dentates, N–S Tetradentates, N–S Pentadentates, or N–S mothioaldehydes, diaZenediacetothioaldehydes, bis(diazen Hexadentates) that meet the requirements for use as “wide ediformothioaldehydes), bis(diazenediacetothioaldehydes), band valence stabilizers for Mn" and/or Mn" include, but poly(diazenediformothioaldehydes), and poly(diazenediac are not limited to: N,N'-(2,5-Thiophenedicarboxaldehydo) 55 diisopropylamine; N.N'-(2,5-Thiophenedicarboxaldehydo) etothioaldehydes) (N–S Tridentates and N—S Hexaden dicyclohexylamine: N,N'-(2,5-Thiophenedicarboxaldehydo) tates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn' include, but are not dianiline; N,N'-(2,5-Thiophenedicarboxaldehydo)di limited to: diazenediformothioaldehyde, diazenediacetothio aminonorbornane; N,N'-(o-Thiophthalicdialdehydo) aldehyde, diphenyldiazenediformothioaldehyde, and diphe diisopropylamine; N,N'-(o-Thiophthalicdialdehydo) 60 dicyclohexylamine; N,N'-(o-Thiophthalicdialdehydo) nyldiazenediacetothioaldehyde. dianiline; N,N'-(o-Thiophthalicdialdehydo)di N—S Valence Stabilizer #22: Examples of ortho-thio (or aminonorbornane; N,N'-(o-Thioformylcamphoro) -mercapto) Substituted formazans, bis(o-thio or -mercapto diisopropylamine; N,N'-(o-Thioformylcamphoro) Substituted formazans), and poly(o-thio or -mercapto Substi dicyclohexylamine; N,N'-(o-Thioformylcamphoro) tuted formazans) (N–S Bidentates, N S Tridentates, N—S 65 dianiline; N,N'-(o-Thioformylcamphoro)di Tetradentates, and N S Hexadentates) that meet the require aminonorbornane; N,N'-(o-Thiodiacetylbenzeno) ments for use as “wide band” valence stabilizers for Mn' diisopropylamine; N,N'-(o-Thiodiacetylbenzeno) US 7,789,958 B2 121 122 dicyclohexylamine; N.N'-(o-Thiodiacetylbenzeno)dianiline: namine)benzyl mercaptain (2-aminomethyl)-alpha-tolu N,N'-(o-Thiodiacetylbenzeno)di-aminonorbornane; N,N'-(3. enethiol (2-mercaptomethyl)-alpha-aminotoluene; 6-Dithio-1,2-cyclohexanono)diisopropylamine; N,N'-(3,6- 1-amino-2-naphthalenethiol: 2-amino-1-naphthalenethiol: Dithio-1,2-cyclohexanono)dicyclohexylamine; N.N'-(3,6- 2-amino-1-(methyldisulfido)benzene: 2,2'-dicaminomethyl) Dithio-1,2-cyclohexanono)dianiline; N.N'-(3,6-Dithio-1,2- diphenylthioketone; di(2-amino)phenyl sulfide; di(2-amino) cyclohexanono)di-aminonorborname; N,N'-(2,5- phenyl disulfide (di-ortho-aminophenyl disulfide (doapd)); Diacetylthiopheno)diisopropylamine; N,N'-(2,5- 1,3-di(2-amino)phenyl-2-mercaptopropane; 1,3-di(3-amino) Diacetylthiopheno)dicyclohexylamine; N,N'-(2,5- phenyl-2-mercaptopropane; 1,3-di(2-mercapto)phenyl-2- Diacetylthiopheno)dianiline; N.N'-(2,5-Diacetylthiopheno) aminopropane; 1,3-di(3-mercapto)phenyl-2-aminopropane; di-aminonorbornane; N,N'-(Thiosalicylaldehydo) 10 2,2'-dimercaptoiminodibenzyl, 2,2'-iminodibenzothioic ethylenediamine; N,N'-(o-Thionaphthaldehydo) acid; 2,2'-dimercaptoiminostilbene; and poly(o-ami ethylenediamine; N,N'-(o-Thioacetophenono) nothiophenol). ethylenediamine; N,N'-(Thiosalicylaldehydo) trimethylenediamine; N,N'-(o-Thionaphthaldehydo) N—S Valence Stabilizer #29. Examples of five-membered trimethylenediamine; N,N'-(o-Thioacetophenono) 15 heterocyclic rings containing one, two, three, or four nitrogen trimethylenediamine; N,N'-(Thiosalicylaldehydo) atoms at least one additional Sulfur atom binding site not in a cyclohexane-1,2-diamine; N,N'-(o-Thionaphthaldehydo) ring (N-S Bidentates, N S Tridentates, N S Tetraden cyclohexane-1,2-diamine; N,N'-(o-Thioacetophenono) tates, or N S Hexadentates) that meet the requirements for cyclohexane-1,2-diamine; N.N'-(Thiosalicylaldehydo)-1,2- use as “wide band valence stabilizers for Mn" and/or Mn" diaminobenzene: N,N'-(o-Thionaphthaldehydo)-1,2- include, but are not limited to: 2-mercaptopyrrole, 2-(meth diaminobenzene; and N,N'-(o-Thioacetophenono)-1,2- ylthio)methylpyrrole; 2.5-(thiomethyl)pyrrole; 2.5-(meth diaminobenzene. Also includes Schiff Bases derived from the ylthiomethyl)pyrrole; 2,6-(methyldisulfidomethyl)pyrrole; reaction of carbonyl compounds with dithiocarbazates, and imidazoline-2-thione (2-mercaptoimidazole); 2-mercap hydrazones with ortho-S substitution. 25 tothiazoline: 2-mercaptobenzimidazole, 2-mercaptoben N–S Valence Stabilizer #26: Examples of Schiff Bases with Zothiazole, 2-mercaptobenzoxazole, 2-thiohydantoin, di-2- three Imine (C—N) Groups and with ortho- or alpha- or pyridylthioglyoxal (2,2'-thiopyridil); bis(1-pyrazolyl) beta-thio or mercapto or thiocarbonyl substitution (N STet methane)sulfide; bis((1-pyrazolyl)methane)disulfide; bis(2- radentates, N S Pentadentates, or N S Hexadentates) that (1-pyrazolyl)ethane)sulfide: bis(2-(1-pyrazolyl)ethane) meet the requirements for use as “wide band valence stabi 30 disulfide; bis(benzimidazolylmethane)sulfide: bis lizers for Mn" and/or Mn" include, but are not limited to: (benzimidazolylethane)sulfide; bis(benzimidazolylmethane) N,N',N'-(Thiosalicylaldehydo)tris(2-aminoethyl)amine: disulfide: bis(benzimidazolylethane)disulfide: tris N,N',N'-(o-Thionaphthaldehydo)tris(2-aminoethyl)amine; (imidazolyl)methanethiol: tris(imidazolylmethane) and N,N',N'-(o-Thioacetophenono)tris(2-aminoethyl) methanethiol: N-thiomethyl-N,N-(benzimidazolylmethane) amine. Also includes Schiff Bases derived from the reaction 35 amine; N-(2-thioethyl)-N,N-(benzimidazolylmethane) of carbonyl compounds with dithiocarbazates, and hydra amine; N.N'-dicbenzimidazolylmethane)-1,3-diamino-2- Zones with ortho-S substitution. mercaptopropane; N,N,N',N'-tetrakis (benzimidazolylmethane)-1,3-diamino-2-mercaptopropane; N—S Valence Stabilizer #27: Examples of thioalkyl amines bis(N.N-((4-imidazolyl)methane)-2-aminoethane)sulfide: (aminothiols or aminodisulfides) and thioalkyl imines (imi 40 bis(N.N-((4-imidazolyl)methane)-2-aminoethane)disulfide: nothiols oriminodisulfides) (N. S. Bidentates, N STriden 2-aminobenzothiazole (abt), 2-phenylaminothiazole; thiohy tates, N S Tetradentates, and N—S Hexadentates) that meet dantoin; thioxohydropyrazole; 2-mercaptobenzothiazole the requirements for use as “wide band valence stabilizers for Mn' and/or Mn' include, but are not limited to: 2-mer (mbt), 2-mercapto-1,3,4-thiadiazole; 2,5-dimercapto-1,3,4- capto-1-aminoethane, 2-methylmercapto-1-aminoethane; thiadiazole (bismuthiol); 2.5-bis(alkylthio)-1,3,4-thiadiaz 3-mercapto-1-aminopropane; 1-mercapto-2-amino-2-meth 45 ole; 2-amino-5-mercapto-1,3,4-thiadiazole (amt); 5-mercap ylpropane: 2-mercaptocyclohexylamine; 3-mercapto-2-ami totetrazole; 1-phenyl-5-mercaptotetrazole (pmt)(5-mptt); nonorbornane; 1,3-dimercapto-2-aminopropane; 1.5-dimer 5-mercaptotriazole: 3-mercaptotriazole; (2-benzothiazolyl) capto-3-aminopentane: 2,2'-diaminodiethyl sulfide: 3,3'- thioacetic acid; (2-benzothiazolyl)thiopropionic acid; (alky diaminodipropyl sulfide: 2,2'-diaminodicyclohexyl sulfide: lthio)benzotriazoles: (arylthio)benzotriazoles; 2-mercapto 1,6-dimercapto-3,4-diaminohexane; 1,7-dimercapto-3,5-di 50 pyrimidine; bis(5-mercapto-1,2,4-triazol-3-yl); bis(5- aminoheptane; 1,6-diamino-3,4-dimercaptohexane; 1,7-di mercapto-1,2,4-triazol-3-yl)alkanes; 2-aminothiazolidine; amino-3,5-dimercaptoheptane; tri(mercaptomethyl)amine; thiazolidine-2-thione, 2-mercaptothiazolidine: 1-(2-mercap tri(2-mercaptoethyl)amine; dithiooxamide (rubeanic acid); toethyl)imidazoline; imidazolidine-2-thione; 4,5-dihydroxy 2,2'-diaminodiethyl disulfide; 3,3'-diaminodipropyl disul imidazolidine-2-thione, 4-amino-5-mercapto-1,2,4-triazole; fide: 2,2'-diaminodicyclohexyl disulfide: 3-amino-1,5-pen 55 (2-benzimidazolylthio)carboxylic acids; (2-benzox tanedithiodialdehyde: 3,4-diamino-1,6-hexanedithiodialde azolylthio)carboxylic acids; (2-benzothiazolylthio)carboxy hyde; 3,5-diamino-1,7-heptanedithiodialdehyde; lic acids; (2-benzimidazolylthio)hydroxyalkyl(aryl)s: iminobisacetic acid; iminobispropionic acid; and bis(hy (2-benzoxazolylthio)hydroxyalkyl (aryl)s; (2-benzothiaz droxyethyl)aminoalkyl sulfide. olylthio)hydroxyalkyl (aryl)s; 2-(phenylmethylthio)ben 60 Zothiazole; 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles: N—S Valence Stabilizer #28: Examples of thioaryl amines 2-(hydrocarbyldithio)-5-mercapto-1,3,4-thiadiazoles; bis and thioaryl imines (N S Bidentates, N S Tridentates, (dithiobisthiadiazole); benzothiazolethione: 3-hydrazino-5- N—S Tetradentates, and N S Hexadentates) that meet the thio-1,2,4-triazole; imidazolidine-2,4-dithione; dimercapto requirements for use as “wide band valence stabilizers for benzothiazole; 2-aminothiazole (atz); thiadiazole-2-thione; Mn" and/or Mn' include, but are not limited to: 2-ami 65 5-mercaptothiadiazole-2-thione; 1,1-thiocarbonyldiimida nothiophenol (2-aminobenzenethiol); 2-aminothiobenzoic Zole; phosphosphonomethylenethio-1,3-benzothiazole acid (thioanthranilic acid), 2-aminothioanisole: 2-(metha (pmtbt); 4,5-dihydroxyimidazolidine-2-thione; imidazoli US 7,789,958 B2 123 124 dine-2-thione; 1,1'-thiocarbonyldiimidazole; 2,2'-dithiobis valence stabilizers for Mn" and/or Mn' include, but are not (benzothiazole); and 5.5'-dithiobis(tetrazole). limited to: 2-(2-thiadiazolyl)benzimidazole: 2-(2-thiophene) pyridine; 2,6-di(2-thiophene)pyridine: 2-(2-thiopyran)pyri N—S Valence Stabilizer #30: Examples of six-membered dine; 2,6-di(2-thiopyran)pyridine; 2,5-di(2-pyridyl) heterocyclic rings containing one, two, three, or four nitrogen thiophene; 2,6-di(2-pyridyl)thiopyran; and 2-(4-thiazolyl) atoms at least one additional Sulfur atom binding site not in a benzimidazole. ring (N-S Bidentates, N S Tridentates, N S Tetraden tates, or N S Hexadentates) that meet the requirements for N SValence Stabilizer #35: Examples of two-, three-, four-, use as “wide band' valence stabilizers for Mn, and/or Mn" six-, eight-, and ten-membered macrocyclics, macrobicy clics, and macropolycyclics (including catapinands, include, but are not limited to: 4-aminomethyl-3-py 10 ridinemethanethiol (including thiopyridoxamine); 2-mercap cryptands, cyclidenes, and sepulchrates) wherein all binding topyridine: 2-(methylthio)methylpyridine: 2-(2-(methylthio) sites are composed of nitrogen (usually amine or imine ethyl)pyridine: 2,6-(thiomethyl)pyridine: 2,6- groups) or Sulfur (usually thiols, mercaptains, or thiocarbon (methylthiomethyl)pyridine; 2,6-(methyldisulfidomethyl) yls) and are not contained in component heterocyclic rings pyridine, 2-mercaptopyrimidine, 2-dithiomethylpyrimidine; 15 (N—S Bidentates, N S Tridentates, N S Tetradentates, and N S Hexadentates) that meet the requirements for use as 2-mercaptoquinoline; 8-mercaptoquinoline (thioxine); 8-me “wide band' valence stabilizers for Mn" and/or Mn" thylthioquinoline: 2-mercaptoquinazoline; thioorotic acid include, but are not limited to: azathiacyclobutane (4an (1,2,3,6-tetrahydro-2,6-dithiono-4-pyrimidinecarboxylic eNS); azathiacyclopentane (5aneNS); azathiacyclohexane acid) (6-thiouracilcarboxylic acid): 1-methylpyrimidine-2- (6aneNS); azathiacycloheptane (7aneNS); azathiacy thione: 2-thiouracil; 2,4-dithiouracil; 6-mercaptopurine; bis clooctane (8aneNS); azathiacyclobutene (4eneNS); aza (N.N.N',N'-tetra(2-(2-pyridyl)ethane)aminomethane)sul thiacyclopentene (5eneNS); azathiacyclohexene (6en fide: bis(N.N.N',N'-tetra(2-(2-pyridyl)ethane) eNS); azathiacycloheptene (7eneNS); azathiacyclooctene aminomethane)disulfide; bis(N.N.N',N'-tetra(2-(2-pyridyl) (8eneNS); azathiacyclobutadiene (4dieneNS); azathiacy ethane)aminoethane)Sulfide; bis(N.N.N',N'-tetra(2-(2- clopentadiene (5dieneNS); azathiacyclohexadiene (I6 di pyridyl)ethane)aminoethane)disulfide; 1,3,5-triazine-6- 25 eneNS); azathiacycloheptadiene (7dieneNS); azathiacy thione: 2-benzylmercapto-1,3,5-triazine; triazine dithiols clooctadiene (8dieneNS): diazathiacyclohexane (I6 i.e. 6-(phenylamino)-1,3,5-triazine-2,4-dithiol (ptd); aneSN); diazathiacycloheptane (7aneSN); 6-aniline-1,3,5-triazine-2,4-dithiol (atd); and 2-(N,N-dialky diazathiacyclooctane (8 laneSN); diazathiacyclononane lamino)-1,3,5-triazine-4,6-dithiol: 2-thioquinazoline; (9aneSN); diazathiacyclodecane (10aneSN): diazathia 2-thioquinazolin-4-one; thiomorpholin-3-thione: 2-(ami 30 cycloundecane (11 laneSN); diazathiacyclododecane (12 nomethyl)thiopyridine; 6-mercaptopurine; dithiouracil; and aneSN): diazathiacyclohexene (6eneSN), diazathiacyclo 2,2'-dithiodipyridine (2,2'-dipyridyl disulfide). heptene (7eneSN); diazathiacyclooctene (8 eneSN); N—S Valence Stabilizer #31: Examples of five-membered diazathiacyclononene (9eneSN); diazathiacyclodecene heterocyclic rings containing one or two Sulfur atoms at least (1OleneSN): diazathiacycloundecene (11eneSN): diaza one additional nitrogenatom binding site not in a ring (N-S 35 thiacyclododecene (12eneSN); diazadithiacyclooctane Bidentates, N S Tridentates, N S Tetradentates, or N–S (8 laneSN); diazadithiacyclononane (9ameSN); diaza Hexadentates) that meet the requirements for use as “wide dithiacyclodecane (10aneSN): diazadithiacycloundecane band valence stabilizers for Mn" and/or Mn" include, but (1 laneSN); diazadithiacyclododecane (12aneSN); are not limited to: 2-aminothiophene; 2,5-diaminothiophene; diazadithiacyclotridecane (13aneSN); diazadithiacy 2-aminomethylthiophene; 2,5-di(aminomethyl)thiophene; 40 clotetradecane (14aneSN); diaZadithiacyclopentadecane 2-aminobenzothiophene; and 2-iminothiolane. (15aneSN); diaZadithiacyclohexadecane (16aneSN); diazadithiacycloheptadecane (17aneSN); diazadithiacy N—S Valence Stabilizer #32: Examples of six-membered clooctadecane (18 aneSN); diazadithiacyclononadecane heterocyclic rings containing one or two Sulfur atoms at least (19aneSN); diazadithiacycloeicosane (20aneSN); one additional nitrogenatom binding site not in a ring (N-S 45 diazadithiacyclooctadiene (8dieneSN); diazadithiacy Bidentates, N S Tridentates, N S Tetradentates, or N–S clononadiene (9dieneSN): diazadithiacyclodecadiene Hexadentates) that meet the requirements for use as “wide (1OdieneSN); diazadithiacycloundecadiene (11 band valence stabilizers for Mn" and/or Mn" include, but dieneSN): diazadithiacyclododecadiene (12dieneSN); are not limited to: 2-aminothiopyran; 2,6-diaminothiopyran: diazadithiacyclotridecadiene (13dieneSN); diazadithia 2-aminomethylthiopyran; 2,6-di(aminomethyl)thiopyran: 50 cyclotetradecadiene (14dieneSN); diazadithiacyclopen and 2-aminobenzothiopyran. tadecadiene (15dieneSN); diazadithiacyclohexadecadi N–S Valence Stabilizer #33: Examples of five-membered ene (16dieneSN); diazadithiacycloheptadecadiene (17 heterocyclic rings containing one, two, three, or four nitrogen dieneSN): diazadithiacyclooctadecadiene (18) atoms at least one additional Sulfur atom binding site in a dieneSN); diazadithiacyclononadecadiene (19) separate ring (N-S Bidentates, N S Tridentates, N S Tet 55 dieneSN): diazadithiacycloeicosadiene (20dieneSN); radentates) that meet the requirements for use as “wide band and tetramethyldithiahexaazacyclobidecanehexaene (mtab). valence stabilizers for Mn" and/or Mn' include, but are not limited to: 2-(2-thiophene)pyrrole; 2,5-di(2-thiophene)pyr N SValence Stabilizer #36: Examples of four-, six-, eight-, role, 2-(2-thiopyran)pyrrole; 2,5-di(2-thiopyran)pyrrole; or ten-membered macrocyclics, macrobicyclics, and 60 macropolycyclics (including catapinands, cryptands, cyclid 2,5-di(2-pyrrole)thiophene; 2,6-di(2-pyrrole)thiopyran; and enes, and sepulchrates) wherein all binding sites are com 3,5-bis(2-thienyl)-4-amino-1,2,4-triazole (2-tat). posed of nitrogen or Sulfur and are contained in component N—S Valence Stabilizer #34: Examples of six-membered heterocyclic rings (N. S. Bidentates, N—S Tridentates, heterocyclic rings containing one, two, three, or four nitrogen N S Tetradentates, or N S Hexadentates) that meet the atoms at least one additional Sulfur atom binding site in a 65 requirements for use as “wide band valence stabilizers for separate ring (N-S Bidentates, N S Tridentates, N S Tet Mn" and/or Mn" include, but are not limited to: dithiopyr radentates) that meet the requirements for use as “wide band andipyridines; dithiophenedipyrroles; trithiopyrantripy US 7,789,958 B2 125 126 ridines; trithiophenetripyrroles; tetrathiopyrantetrapyridines; and N—O Tetradentates) that meet the requirements for use and tetrathiophenetetrapyrroles. as “wide band' valence stabilizers for Mn" and/or Mn" include, but are not limited to: guanylurea (amidinourea) N—SValence Stabilizer #37: Examples of four-, six-, eight-, (dicyandiamidine); guanidinourea; methylguanylurea; eth or ten-membered macrocyclics, macrobicyclics, and 5 ylguanylurea; isopropylguanylurea; butylguanylurea; ben macropolycyclics (including catapinands, cryptands, cyclid Zylguanylurea; phenylguanylurea; tolylguanylurea; enes, and sepulchrates) wherein all binding sites are com naphthylguanylurea; cyclohexylguanylurea; norbornylgua posed of nitrogen or Sulfur and are contained in a combination nylurea; adamantylguanylurea; dimethylguanylurea; dieth of heterocyclic rings and amine, imine, thiol, mercapto, or ylguanylurea; diisopropylguanylurea; dibutylguanylurea; thiocarbonyl groups (N-S Bidentates, N S Tridentates, 10 dibenzylguanylurea; diphenylguanylurea; ditolylguanylurea; N—S Tetradentates, or N S Hexadentates) that meet the dinaphthylguanylurea; dicyclohexylguanylurea; dinor requirements for use as “wide band valence stabilizers for bornylguanylurea; diadamantylguanylurea; ethylenebis(gua Mn" and/or Mn' include, but are not limited to: azathiatet nylurea); propylenebis(guanylurea); phenylenebis(guany raphyrins; diazadithiatetraphyrins; azathiahexaphyrins; lurea); piperazinebis(guanylurea); oxalylbis(guanylurea); diazadithiahexaphyrins; and triaZatrithiahexaphyrins. 15 malonylbis(guanylurea); Succinylbis(guanylurea); phthalyl N—O Valence Stabilizer #1: Examples of N-hydroxy(or bis(guanylurea); 2-ureidothiazole; 2-ureidooxazole; 2-ure N,N'-dihydroxy)amidines and N-hydroxy(or N,N'-dihy idoimidazole, 3-ureidopyrazole; 3-ureido-1,2,4-triazole; and droxy)diamidines (N-O bidentates, N—O tridentates, or 5-ureidotetrazole. N—O tetradentates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn" N O Valence Stabilizer #3: Examples of amidinoamides, include, but are not limited to: N-hydroxy-N,N'-dimethylfor guanidinoamides, bis(amidinoamides), bis(guanidinoam mamidine: N-hydroxy-N,N'-diethylformamidine; N-hy ides), poly(amidinoamides), and poly(guanidinoamides) (in droxy-N,N'-diisopropylformamidine: N-hydroxy-N,N'- cluding both N-amidinoamides and 2-amidinoacetamides) dibutyl formamidine: N-hydroxy-N,N'- (N—O Bidentates, N O Tridentates, and N O Tetraden diphenylformamidine; N-hydroxy-N,N'- 25 tates) that meet the requirements for use as “wide band dibenzylformamidine: N-hydroxy-N,N'- valence stabilizers for Mn" and/or Mn" include, but are not dinaphthylformamidine: N-hydroxy-N,N'- limited to: amidinoacetamide (1-acetylguanidine); guanidi dicyclohexylformamidine: noacetamide; amidinopropanamide; amidinobutanamide; dinorbornylformamidine: amidinobenzamide; amidinotoluamide; amidinocyclohexa diadamantylformamidine; N-hydroxy-N,N'- 30 mide; N-methylamidinoacetamide; N-ethylamidinopropana dianthraquinonylformamidine; N-hydroxy-N,N'- mide: N-propylamidinobutanamide; N-phenylamidinoben dimethylacetamidine: N-hydroxy-N,N'-diethylacetamidine: Zamide: N-tolylamidinotoluamide: N-hydroxy-N,N'-diisopropylacetamidine; N-hydroxy-N,N'- N-cyclohexylamidinocyclohexamide; bis(amidinooxamide); dibutylacetamidine; N-hydroxy-N,N'-diphenylacetamidine: bis(amidinomalonamide); bis(amidinosuccinamide); bis N-hydroxy-N,N'-dibenzylacetamidine; N-hydroxy-N,N'-di 35 (amidinophthalamide); 2-amidinoacetamide (malonamami naphthylacetamidine; N-hydroxy-N,N'-dicyclohexylaceta dine); N-methyl-2-amidinoacetamide: N-ethyl-2-amidinoac midine: N-hydroxy-N,N'-dinorbornylacetamidine; N-hy etamide: N-phenyl-2-amidinoacetamide: N-benzyl-2- droxy-N,N'-diadamantylacetamidine; N-hydroxy-N,N'- amidinoacetamide; N-cyclohexyl-2-amidinoacetamide; dimethylbenzamidine: N-hydroxy-N,N'- N,N'-dimethyl-2-amidinoacetamide: N,N'-diethyl-2-amidi diethylbenzamidine: N-hydroxy-N,N'- 40 noacetamide: N,N'-diphenyl-2-amidinoacetamide: N,N'- diisopropylbenzamidine; N-hydroxy-N,N'- dibenzyl-2-amidinoacetamide: N,N'-dicyclohexyl-2-amidi dibutylbenzamidine: N-hydroxy-N,N'- noacetamide; 2-N-acylaminothiazole; 2-N- diphenylbenzamidine; N-hydroxy-N,N'- acylaminooxazole; 2-N-acylaminoimidazole; 3-N- dibenzylbenzamidine; N-hydroxy-N,N'- acylaminopyrazole; 3-N-acylamino-1,2,4-triazole; and 5-N- dinaphthylbenzamidine; N-hydroxy-N,N'- 45 acylaminotetrazole. dicyclohexylbenzamidine: N-hydroxy-N,N'- N O Valence Stabilizer #4: Examples of imidoylamides, dinorbornylbenzamidine; N-hydroxy-N,N'- bis(imidoylamides), and poly(imidoylamides) (N O Biden diadamantylbenzamidine; N-hydroxy-N, tates, N—O Tridentates, and N—O Tetradentates) that meet N'dimethyltoluamidine: N-hydroxy-N,N'- the requirements for use as “wide band valence stabilizers diethyltoluamidine: N-hydroxy-N,N'- 50 for Mn" and/or Mn' include, but are not limited to:acetimi diisopropyltoluamidine; N-hydroxy-N,N'- doylacetamide; acetimidoylpropanamide; acetimidoylbu dibutyltoluamidine; N-hydroxy-N,N'-diphenyltoluamidine: tanamide; acetimidoylbenzamide; acetimidolytoluamide; N-hydroxy-N,N'-dibenzyltoluamidine: N-hydroxy-N,N'-di acetimidoylcyclohexamide; propimidoylpropanamide: naphthyltoluamidine; N-hydroxy-N,N'-dicyclohexyltolua butimidoylbutanamide; benzimidoylbenzamide; ethylenebis midine: N-hydroxy-N,N'-dinorbornyltoluamidine; N-hy 55 (acetimidoylacetamide); propylenebis(acetimidoylaceta droxy-N,N'-diadamantyltoluamidine; N.N-dihydroxyoxalic mide); and phenylenebis(acetimidoylacetamide). diamidine; N.N'-dihydroxymalonic diamidine: N,N'-dihy droxysuccinic diamidine; N.N'-dihydroxyglutaric diamidine: N OValence Stabilizer #5: Examples of O-amidinocarbam N,N'-dihydroxyadipic diamidine; N.N'-dihydroxypimelic ates, bis(O-amidinocarbamates), and poly(O-amidinocar 60 bamates) (N O Bidentates and N—O Tetradentates) that diamidine; N,N'-dihydroxysuberic diamidine; N.N'-dihy meet the requirements for use as “wide band valence stabi droxyphthalic diamidine: N,N'-dihydroxyterephthalic diami lizers for Mn" and/or Mn" include, but are not limited to: dine: N,N'-dihydroxyisophthalic diamidine: N,N'-dihydrox O-amidinocarbamate; N-methyl-O-amidinocarbamate; ypiperazine diamidine. N-ethyl-O-amidinocarbamate; N-isopropyl-O-amidinocar N—O Valence Stabilizer #2: Examples of guanylureas, 65 bamate; N-butyl-O-amidinocarbamate; N-benzyl-O-amidi guanidinoureas, bis(guanylureas), bis(guanidinoureas), poly nocarbamate; N-phenyl-O-amidinocarbamate; N-tolyl-O- (guanylureas), and poly(guanidinoureas) (N-O Bidentates amidinocarbamate; N-naphthyl-O-amidinocarbamate; US 7,789,958 B2 127 128 N-cyclohexyl-O-amidinocarbamate; N-norbornyl-O-amidi acid), and derivatives thereof (N, O Bidentates, N—O Tet nocarbamate; N-adamantyl-O-amidinocarbamate; N.N'- radentates) that meet the requirements for use as “wide band dimethyl-O-amidinocarbamate; N.N'-diethyl-O-amidinocar valence stabilizers for Mn" and/or Mn" include, but are not bamate; N.N'-diisopropyl-O-amidinocarbamate; N.N'- limited to: phosphorimidic acid; O-phenylphosphorimidic dibutyl-O-amidinocarbamate; N,N'-dibenzyl-O- acid; O-benzylphosphorimidic acid; O-cyclohexylphospho amidinocarbamate; N.N'-diphenyl-O-amidinocarbamate: rimidic acid; O-norbornylphosphorimidic acid; O,O'-diphe N,N'-ditolyl-O-amidinocarbamate: N,N'-dinaphthyl-O-ami nylphosphorimidic acid; O,O'-dibenzylphosphorimidic acid; dinocarbamate; N.N'-dicyclohexyl-O-amidinocarbamate: O.O'-dicyclohexylphosphorimidic acid; and O,O'-dinor N,N'-dinorbornyl-O-amidinocarbamate; N.N'-diadamantyl bornylphosphorimidic acid. O-amidinocarbamate; ethylenebis(O-amidinocarbamate); 10 propylenebis(O-amidinocarbamate); phenylenebis(O-amidi N O Valence Stabilizer #9: Examples of phosphoric tria nocarbamate); piperazinebis(O-amidinocarbamate); oxalyl mides, bis(phosphoric triamides), and poly(phosphoric tria bis(O-amidinocarbamate); malonylbis(O-amidinocarbam mides) (N O Bidentates and N—O Tetradentates) that meet ate); succinylbis(O-amidinocarbamate); phthalylbis(O- the requirements for use as “wide band valence stabilizers amidinocarbamate); 2-O-carbamatothiazole; 2-O- 15 for Mn" and/or Mn" include, but are not limited to: phos carbamatooxazole; 2-O-carbamatoimidazole; 3-O- phoric triamide: phosphoramidic dihydrazide. N-phe carbamatopyrazole, 3-O-carbamato-1,2,4-triazole; and nylphosphoric triamide, N-benzylphosphoric triamide: N-cy 5-carbamatotetrazole. clohexylphosphoric triamide: N-norbornylphosphoric triamide: N,N'-diphenylphosphoric triamide, N,N'-diben N—O Valence Stabilizer #6: Examples of S-amidinothiocar Zylphosphoric triamide: N,N'-dicyclohexylphosphoric tria bamates, bis(S-amidinothiocarbamates), and poly(S-amidi mide; and N,N'-dinorbornylphosphoric triamide. nothiocarbamates) (N-O Bidentates and N—O Tetraden tates) that meet the requirements for use as “wide band N O Valence Stabilizer #10: Examples of phosphoramidic valence stabilizers for Mn" and/or Mn' include, but are not acid, phosphorodiamidic acid, bis(phosphoramidic acid), bis limited to: S-amidinothiocarbamate; N-methyl-S-amidi 25 (phosphorodiamidic acid), poly(phosphoramidic acid), poly nothiocarbamate; N-ethyl-S-amidinothiocarbamate; N-iso (phosphorodiamidic acid), and derivatives thereof (N O propyl-S-amidinothiocarbamate; N-butyl-S-amidinothiocar Bidentates and N O Tetradentates) that meet the require bamate; N-benzyl-S-amidinothiocarbamate; N-phenyl-S- ments for use as “wide band” valence stabilizers for Mn' amidinothiocarbamate; N-tolyl-S-amidinothiocarbamate: and/or Mn" include, but are not limited to: phosphoramidic N-naphthyl-S-amidinothiocarbamate; N-cyclohexyl-S-ami 30 acid, phosphorodiamidic acid, phosphoramidohydrazidic dinothiocarbamate; N-norbornyl-S-amidinothiocarbamate: acid; phosphorohydrazidic acid; phosphorodihydrazidic N-adamantyl-S-amidinothiocarbamate: N,N-dimethyl-S- acid; O-phenylphosphoramidic acid; O-benzylphosphora amidinothiocarbamate; N.N'-diethyl-S-amidinothiocarbam midic acid; O-cyclohexylphosphoramidic acid; O-nor ate; N.N'-diisopropyl-S-amidinothiocarbamate; N.N'-dibu bornylphosphoramidic acid; O,O'-diphenylphosphoramidic tyl-S-amidinothiocarbamate; N,N'-dibenzyl-S- 35 amidinothiocarbamate; N,N'-diphenyl-S- acid; O,O'-dibenzylphosphoramidic acid; O,O'-dicyclohexy amidinothiocarbamate; N,N'-ditolyl-S- lphosphoramidic acid; and O,O'-dinorbornylphosphoramidic amidinothiocarbamate; N,N'-dinaphthyl-S- acid. amidinothiocarbamate; N,N'-dicyclohexyl-S- N O Valence Stabilizer #11: Examples of N-acyl 7-ami amidinothiocarbamate; N,N'-dinorbornyl-S- 40 nobenzylidenimines (N O Bidentates or N O Tetraden amidinothiocarbamate; N,N'-diadamantyl-S- tates) that meet the requirements for use as “wide band amidinothiocarbamate; ethylenebis(S- valence stabilizers for Mn" and/or Mn' include, but are not amidinothiocarbamate); propylenebis limited to: N-acetyl 7-methylaminobenzylidenimine: (S-amidinothiocarbamate); phenylenebis (S-amidinothiocar N-acetyl 7-phenylaminobenzylidenimine; N-benzoyl 7-me bamate); piperazinebis(S-amidinothiocarbamate); oxalylbis 45 thylaminobenzylidenimine; and N-benzoyl 7-phenylami (S-amidinothiocarbamate); malonylbis (S-amidinothiocar nobenzylidenimine. bamate); succinylbis (S-amidinothiocarbamate); phthalylbis (S-amidinothiocarbamate); 2-O- N O Valence Stabilizer #12: Examples of oximes, monothiocarbamatothiazole; 2-O- dioximes, and poly(oximes) (N O Bidentates, N—O Tri monothiocarbamatooxazole; 2-O- 50 dentates, and N—O Tetradentates) that meet the requirements monothiocarbamatoimidazole; 3-O- for use as “wide band” valence stabilizers for Mn" and/or monothiocarbamatopyrazole; 3-O-monothiocarbamato-1.2. Mn" include, but are not limited to: acetaldoxime (Hado); 4-triazole; and 5-O-monothiocarbamatotetrazole. acetoxime (acetone oxime)(Hato); butanone oxime; pen N—O Valence Stabilizer #7: Examples of diimidosulfuric tanone oxime; hexanone oxime; pinacolone oxime; hep 55 tanone oxime; octanone oxime; cyclopentanone oxime; acid, bis(diimidosulfuric acid), and derivatives thereof cyclohexanone oxime; cycloheptanone oxime; cyclooc (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band valence stabilizers for tanone oxime; cyclopentanedione dioxime; cyclohexanedi Mn" and/or Mn" include, but are not limited to: diimidosul one dioxime; cycloheptanedione dioxime; cyclooctanedione furic acid; O-phenyldiimidosulfuric acid; O-benzyldiimi dioxime; isatin dioxime; benzaldehyde Oxime; naphthalde dosulfuric acid, O-cyclohexyldiimidosulfuric acid, O-nor 60 hyde oxime; norbornanone oxime; camphor oxime; dimeth bornyldiimidosulfuric acid, O.O'-diphenyldiimidosulfuric ylglyoxime (HDMG); diethylglyoxime; diisopropylgly acid; O,O'-dibenzyldiimidosulfuric acid, O.O'-dicyclohexyl Oxime; ditertbutylglyoxime; dicyanoglyoxime; diimidosulfuric acid, and O,O'-dinorbornyldiimidosulfuric dicyanamidoglyoxime; diphenylglyoxime (Hdfg); diben acid. Zylglyoxime; dicyclohexylglyoxime; dinorbornylglyoxime; 65 camphorquinone dioxime (HCqd); nopinoquinone dioxime N—O Valence Stabilizer #8: Examples of phosphorimidic (Hnqd); butyraldoxime; propionaldoxime; furildioxime; and acid, bis(phosphorimidic acid); and poly(phosphorimidic thienyldioxime. US 7,789,958 B2 129 130 N—OValence Stabilizer #13: Examples of carbonyl oximes, tates, N. O Tridentates, N-O Tetradentates, and N—O bis(carbonyl oximes), and poly(carbonyl oximes) (N O Hexadentates) that meet the requirements for use as “wide Bidentates, N OTridentates, and N O Tetradentates) that band valence stabilizers for Mn" and/or Mn" include, but meet the requirements for use as “wide band valence stabi are not limited to: 3-(methylamino)butan-2-one oxime lizers for Mn" and/or Mn" include, but are not limited to: (HMeabo): 4-(methylamino)hexan-3-one oxime (HEtabo); diacetyl monoxime (2,3-butanedione monoxime); benzil 1,2-diphenyl-2-(methylamino)ethanone oxime (HPhabo); monoxime (1,2-diphenylethanedione monoxime); 1,2-dicy 1.2-diphenyl-2-(phenylamino)ethanone oxime; 1,2-dicyclo clohexylethanedione monoxime; 1.2-(trifluoromethyl) hexyl-2-(methylamino)ethanone oxime (Hey Hxabo); 1,2-di ethanedione monoxime; 1,2-dinorbornylethanedione mon cyclohexyl-2-(cyclohexylamino)ethanone oxime; 1,2-di(tri 10 fluoromethyl)-2-(methylamino)ethanone oxime; 1.2- Oxime; cyclopentanedione monoxime; cyclohexanedione dinorbornyl-2-(methylamino)ethanone oxime (HNorbabo); monoxime; cycloheptanedione monoxime; cyclooctanedi N,N'-ethylenebis-(3-aminobutan-2-one oxime)(Haboen); one monoxime; camphorquinone oXime: 3-hydroxyimino N,N'-ethylenebis-(4-aminohexan-3-one oxime); N,N'-ethyl pentane-2,4-dione; and 4-isonitrosopyraloZone. enebis-(1,2-diphenyl-2-aminoethanone oxime); N,N'-ethyl N—O Valence Stabilizer #14: Examples of imine oximes, 15 enebis-(1,2-dicyclohexyl-2-aminoethanone oxime); N,N'- bis(imine oximes), and poly(imine oximes) (including 2-ni ethylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone trogen heterocyclic oximes) (N O Bidentates, N—O Tri oxime); N,N'-ethylenebis-(1,2-dinorbornyl-2-aminoetha dentates, N O Tetradentates, and N—O Hexadentates) that none oxime); N,N'-propylenebis-(3-aminobutan-2-one meet the requirements for use as “wide band valence stabi oxime)(Habopn); N,N'-propylenebis-(4-aminohexan-3-one lizers for Mn" and/or Mn" include, but are not limited to: oxime); N,N'-propylenebis-(1,2-diphenyl-2-aminoethanone 3-(methylimino)butan-2-one oxime, 4-(methylimino)hexan oxime); N,N'-propylenebis-(1,2-dicyclohexyl-2-aminoetha 3-one oxime; 1,2-diphenyl-2-(methylimino)ethan-1-one none oxime); N,N'-propylenebis-(1,2-di(trifluoromethyl)-2- Oxime; 1,2-diphenyl-2-(phenylimino)ethan-1-one oxime; aminoethanone oxime); N,N'-propylenebis-(1,2-dinor 1.2-dicyclohexyl-2-(methylimino)ethan-1-one oxime; 1.2- bornyl-2-aminoethanone Oxime); 2,2'-iminobis dicyclohexyl-2-(cyclohexylimino)ethan-1-one oxime; 1.2- 25 (acetamidoxime); 1-diethylamino-3-butanoxime; and di-2- dinorbornyl-2-(methylimino)ethan-1-one oxime; N.N'-me pyridyl ketone oxime. thylenebis-(3-iminobutan-2-one Oxime); N,N'- methylenebis-(4-iminohexan-3-one Oxime); N,N'- N O Valence Stabilizer #17: Examples of amido oximes, methylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime); bis(amido oximes), and poly(amido oximes) (N O Biden N,N'-methylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one 30 tates, N. O Tridentates, N-O Tetradentates, and N—O oxime); N,N'-methylenebis-(1,2-dinorbornyl-2-iminoethan Hexadentates) that meet the requirements for use as “wide 1-one oxime); N,N'-ethylenebis-(3-iminobutan-2-one band valence stabilizers for Mn" and/or Mn" include, but oxime); N,N'-ethylenebis-(4-iminohexan-3-one oxime); are not limited to: formamide oxime; acetamide oxime; pro N,N'-ethylenebis-(1,2-diphenyl-2-iminoethan-1-one panamide oxime; butanamide oxime; benzamide oxime oxime); N,N'-ethylenebis-(1,2-dicyclohexyl-2-iminoethan 35 (Hbamox), naphthamide oxime; diformamide dioxime; Sali 1-one oxime); N,N'-ethylenebis-(1,2-dinorbornyl-2-iminoet cylamide oxime; and 4-imidazolamide oxime. han-1-one oxime); N,N'-propylenebis-(3-iminobutan-2-one N O Valence Stabilizer #18: Examples of azo oximes, bis oxime); N,N'-propylenebis-(4-iminohexan-3-one oxime); (aZo oximes), and poly(aZo oximes) (N-O Bidentates, N,N'-propylenebis-(1,2-diphenyl-2-iminoethan-1-one N—OTridentates, N. O Tetradentates, and N—O Hexaden oxime); N,N'-propylenebis-(1,2-dicyclohexyl-2-iminoet 40 tates) that meet the requirements for use as “wide band han-1-one oxime); N,N'-propylenebis-(1,2-dinorbornyl-2- valence stabilizers for Mn" and/or Mn' include, but are not iminoethan-1-one oxime); diacetylazine oxime (Hazio); limited to: acetaldehyde phenylhydrazone oxime; propional 2-pyridinaldoxime (Hpao); methyl 2-pyridyl ketone oxime; dehyde phenylhydrazone oxime; and benzaldehyde phenyl ethyl 2-pyridyl ketoxime; phenyl 2-pyridyl ketone oxime hydrazone oxime. Also includes hydrazone oximes. (Hippk); benzyl 2-pyridyl ketoxime; di(2-pyridyl) ketone 45 N O Valence Stabilizer #19. Examples of 2-nitrosophenols oxime; methyl 2-pyrrolyl ketone oxime; ethyl 2-pyrrolyl (o-quinone monoximes) (N O Bidentates) that meet the ketone oxime; phenyl 2-pyrrolyl ketone oxime; di(2-pyrro requirements for use as “wide band valence stabilizers for lyl) ketone oxime; and tris(2-aldoximo-6-pyridyl)phosphine. Mn" and/or Mn" include, but are not limited to: 2-nitros N—O Valence Stabilizer #15: Examples of hydroxy oximes, ophenol; 1-nitroso-2-naphthol (Honn); 2-nitroso-1-naphthol bis(hydroxy oximes), and poly(hydroxy Oximes) (including 50 (Htnn); 3-nitrosopyrocatechol; 3,6-dinitrosopyrocatechol; 2-oxygen heterocyclic oximes) (N O Bidentates, N OTri 2-nitrosoresorcinol; 2,4-dinitrosoresorcinol; 2.4.6-trini dentates, N O Tetradentates, and N—O Hexadentates) that troSoresorcinol; 2-nitroSohydroquinone; 2,6-dinitrosohydro meet the requirements for use as “wide band valence stabi quinone; 2,3,5,6-tetranitrosohydroquinone: 4-nitrosopyro lizers for Mn" and/or Mn" include, but are not limited to: gallol, 4,6-dinitrosopyrogallol, 2-nitrosophloroglucinol; 2.4. 3-hydroxybutan-2-one oxime: 4-hydroxyhexan-3-one 55 6-trinitrosophloroglucinol; 7-nitroso-6-hydroxyindazole; Oxime; benzoin oxime (bo)(1,2-diphenyl-2-hydroxyetha Pigment Green 12 (C.I. 10020): Naphthol Green; and nitroso none oxime); 1,2-di(trifluoromethyl)-2-hydroxyethanone R-salt. Oxime; 1,2-dicyclohexyl-2-hydroxyethanone oxime; 1,2-di norbornyl-2-hydroxyethanone oxime; salicylaldoxime (so) N O Valence Stabilizer #20: Examples of 2-nitrophenols (saldox); 2-hydroxy-1-naphthaldehyde Oxime; 2-furanal 60 (N—O Bidentates) that meet the requirements for use as doxime; furildioxime; methyl 2-furanyl ketone oxime; ethyl “wide band' valence stabilizers for Mn" and/or Mn" 2-furanyl ketoxime; phenyl 2-furanyl ketone oxime; benzyl include, but are not limited to: 2-nitrophenol; 2.3-dinitrophe 2-furanyl ketoxime; di(2-furanyl) ketone oxime; and 2.5- noli; 2,4-dinitrophenol; 2.5-dinitrophenol; 2,6-dinitrophenol; (oximinomethyl)phenol. 2,4,6-trinitrophenol (picric acid); 2-amino-4,6-dinitrophenol 65 (picramic acid): 1-nitro-2-naphthol; 2-nitro-1-naphthol, 3-ni N—O Valence Stabilizer #16: Examples of amino oximes, tropyrocatechol; 3,6-dinitropyrocatechol; 2-nitroresorcinol; bis(amino oximes), and poly(amino oximes) (N-O Biden 2,4-dinitroresorcinol; 2,4,6-trinitroresorcinol (styphnic US 7,789,958 B2 131 132 acid); 2-nitrohydroquinone; 2,6-dinitrohydroquinone; 2.3.5. N O Valence Stabilizer #24: Examples of amides, bis(a- 6-tetranitrohydroquinone: 4-nitropyrogallol, 4,6-dinitropy mides), and poly(amides), including lactams (N-O biden rogallol; 2-nitrophloroglucinol; 2,4,6-trinitrophloroglucinol; tates, N O tridentates, and N—O tetradentates) that meet dinitrocresol; 7-nitro-6-hydroxyindazole; Dinoseb; Eosin; the requirements for use as “narrow band valence stabilizers Naphthol Yellow; and Martius Yellow. for Mn" and/or Mn" include, but are not limited to: aceta mide; propionamide; butanamide; benzamide (benzoyla N—O Valence Stabilizer #21: Examples of hydroxamates mide)(1-phenylformamide), 1-naphthylformamide; tolua (hydroxylamines), bis(hydroxamates), and poly(hydroxam mide: 1-cyclohexylformamide); 1-norbornylformamide: ates) (N O Bidentates, N. O Tetradentates, and N—O 1-adamantylformamide: N,N-dimethylformamide (DMF) Hexadentates) that meet the requirements for use as “wide 10 (DMFA); N,N-dimethylacetamide (DMAC); N,N-dimethyl band' valence stabilizers for Mn" and/or Mn" include, but benzamide: N,N-diethylformamide: N,N-diethylacetamide: are not limited to: acetohydroxamic acid; propianohydrox decanamide; dodecanamide; tetradecanamide; hexadecana amic acid; butyrohydroxamic acid; crotonohydroxamic acid; mide; octadecanamide; lactobionic acid amide; (hydroxy Sorbohydroxamic acid; benzohydroxamic acid (BH): alkylthio)Succinamides; (mercaptoalkoxy)Succinamides; toluichydroxamic acid; salicylhydroxamic acid (SH); phe 15 polycaproamides; glycinamide; aminoalkylanilides; ami nylacetohydroxamic acid (PhPI); anthranilhydroxamic acid dopolyamines (apa); bis(1-phenylethylamide); Oxalic semia (Anh.); nicotinehydroxamic acid (Nich); picolinehydrox mide; malonic semiamide, Succinic semiamide; bis(1,1'-ben amic acid; cyclohexanehydroxamic acid (CH), quinoline Zotriazolyl)dicarboxamide; nicotinamide; acetanilide 8-hydroxamic acid (QH2): cinnamylhydroxamic acid (N-phenylacetamide); formanilide (N-phenylformamide); benzanilide (N-phenylbenzamide); N-methylformanilide; (CnH); oxaldihydroxamic acid (OxalH); succinylbis-N- acetanilide; nicotinanilide; 4'-hydroxyacetanilide (acetami phenylhydroxamic acid (SuH); adipylbis-N-phenylhydrox nophen); 2-pyrrolidone; methyl-2-pyrrolidone (NMP); 2-pi amic acid (AdRI); glyoxalhydroxamic acid (GH2); peridone (Valerolactam); caprolactam; polymethylenep 2-thiophenecarbohydroxamic acid; thenoylhydroxamic acid; olyamine dipropionamide; polyacrylamides; N-phenylbenzohydroxamic acid; N-tolylbenzohydroxamic 25 polypyrrolidones including polyvinylpyrrolidone (povi acid; N-phenylacetohydroxamic acid; N-phenyl-2-thenoyl done)(PVP); pyrazolidinones; pyrazolones; diazepinones; hydroxamic acid; N-tolyl-2-thenoylhydroxamic acid; and N-alkylazaalkene lactams; and N-(2-hydroxyalkyl)azaalkene polyhydroxamic acids. lactams. N—O Valence Stabilizer #22: Examples of N-nitrosohy N O Valence Stabilizer #25: Examples of semicarbazones, droxylamines, bis(N-nitrosohydroxylamines), and poly(N- 30 bis(semicarbazones), and poly(semicarbazones) (N-O nitrosohydroxylamines) (N O Bidentates, N. O Tetraden Bidentates, N. O Tetradentates, and N O Hexadentates) tates, and N—O Hexadentates) that meet the requirements for that meet the requirements for use as “wide band valence use as “wide band valence stabilizers for Mn" and/or Mn" stabilizers for Mn" and/or Mn' include, but are not limited include, but are not limited to: N-nitrosophenylhydroxy to: acetaldehyde semicarbazone; acetone semicarbazone; lamine (cupferron); N-nitroSonaphthylhydroxylamine (neo 35 pinacolone semicarbazone; benzaldehyde semicarbazone; cupferron); N-nitrosoanthracylhydroxylamine; N-nitroso(2- naphthaldehyde semicarbazone; norbornanone semicarba pyridyl)hydroxylamine; and N-nitroso(2-thiophenyl) Zone; camphor semicarbazone; nopinone semicarbazone; hydroxylamine. 2-pyridinaldehyde semicarbazone; Salicylaldehyde semicar baZone; quinolinaldehyde semicarbazone; isatin disemicar N—O Valence Stabilizer #23: Examples of amino acids, 40 baZone; camphorquinone disemicarbazone; camphorquinone ortho-aminocarboxylic acids, peptides, polypeptides, and disemicarbazone; picolinaldehyde semicarbazone; dipyridyl proteins N O Bidentates, N O Tridentates, and N—O glyoxal disemicarbazone; di-2-pyridyl ketone semicarba Tetradentates; possibly S O dentates for sulfur-contg. Zone; methyl-2-pyridyl ketone semicarbazone; glyoxal dis examples such as penicillamine and cystine that meet the emicarbazone; acetophenone semicarbazone; biacetyl mon requirements for use as “wide band valence stabilizers for 45 Oxime semicarbazone; acetamidobenzaldehyde Mn" and/or Mn' include, but are not limited to: alanine semicarbazone; thymolaldosemicarbazone; thiophene-2-al (Ala); arginine (Arg); asparagine (Asn); aspartic acid (Asp); dehyde semicarbazone; phthalaldehyde disemicarbazone; cysteine (Cys); cystine (CyS or CyS.CyS), dihydroxypheny phthalimide disemicarbazone; furaldehyde semicarbazone; lalanine (Dopa); glutamic acid (Glu); glutamine (Gln); gly naphthoduinone semicarbazone; phenanthrequinone semi cine (Gly); histidine (His); isoleucine (Ile); leucine (Leu); 50 lysine (Lys); methionine (Met); penicillamine (Pen); pheny carbazone; cyclohexanedione disemicarbazone; ionone lalanine (Phe); tolylalanine (tala); proline (Pro); sarcosine: semicarbazone; bissemicarbazone of diethyl-3,4-dioxadio serine (Ser); threonine (Thr); tryptophan (Trp); tyrosine ate; and lawsone semicarbazone. (Tyr); and valine (Val) as amino acid examples; 2-pyridin N O Valence Stabilizer #26: Examples of acyl hydrazones, ecarboxylic acid (picolinic acid), 2-pyrazinecarboxylic acid, 55 bis(acyl hydrazones), and poly(acyl hydrazones) (N-O 2,3-dicarboxypyrazine, and anthranilic acid as ortho-ami Bidentates, N O Tetradentates, and N O Hexadentates) nocarboxylic acid examples; Gly-Gluo; Hgly-Gly; Gly that meet the requirements for use as “wide band valence MetO; Met-GlyO; Gly-Tyro: Ala-H is O: Gly-His-GlyO: stabilizers for Mn" and/or Mn' include, but are not limited Gly-Gly-His; Gly-Leu-Tyro: penta-GlyO: His-His; triami to: acetaldehyde N-formylhydrazone; acetaldehyde N-ben noisobutyrate; tetra-GlyO; Pro-Gly; and Gly-Met as peptide 60 Zoylhydrazone; acetone N-formylhydrazone; acetone N-ben examples; and azurin, carbonic anhydrase C. carboxypepti ZoylhydraZone; pinacolone N-formylhydrazone; pinacolone dase; concanavalin A; cytochrome b; cytochrome c, erythro N-benzoylhydrazone; benzaldehyde N-formylhydrazone: cruorin; ferredoxin; haemerythrin; haemoglobin; myoglobin; benzaldehyde N-benzoylhydrazone; naphthaldehyde parvalbumin; albumin; plastocyanin; rubredoxin; Superoxide N-formylhydrazone; naphthaldehyde N-benzoylhydrazone: dismutase; thermolysin; and trysin as protein examples: 65 norbornanone N-formylhydrazone; norbornanone N-ben N-acylamino acids; aminocaproic acid; and 3,5-diiodoty ZoylhydraZone; camphor N-formylhydrazone; camphor rosine. N-benzoylhydrazone; nopinone N-formylhydrazone; nopi US 7,789,958 B2 133 134 none N-benzoylhydrazone: 2-pyridinaldehyde N-formylhy Mn" and/or Mn' include, but are not limited to: diazenefor drazone: 2-pyridinaldehyde N-benzoylhydrazone; salicylal mic acid, diaZeneacetic acid, phenyldiaZeneformic acid, dehyde N-formylhydrazone; salicylaldehyde diphenyldiazeneformic acid, phenyldiazeneacetic acid, and N-benzoylhydrazone; quinolinaldehyde N-formylhydra diphenyldiazeneacetic acid. Zone; quinolinaldehyde N-benzoylhydrazone; furan-2-alde hyde N-formylhydrazone; furan-2-aldehyde N-benzoylhy N OValence Stabilizer #31: Examples of diazeneformalde draZone; naphthoduinone N-formylhydrazone: hydes, diaZeneacetaldehydes, bis(diaZeneformaldehydes), naphthoquinone N-benzoylhydrazone; ionone N-formylhy bis(diazeneacetaldehydes), poly(diaZeneformaldehydes), drazone; ionone N-benzoylhydrazone; lawsone N-formylhy and poly(diazeneacetaldehydes) (N O Bidentates, N O draZone; and lawsone N-benzoylhydrazone. 10 Tetradentates and N—O Hexadentates) that meet the require ments for use as “wide band valence stabilizers for Mn" N—O Valence Stabilizer #27: Examples of carbazones (dia and/or Mn include, but are not limited to: diazeneformal Zenecarboxylic hydrazides), bis(carbazones), and poly(car dehyde, diaZeneacetaldehyde, phenyldiazeneformaldehyde, bazones) (N O Bidentates, N. O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide diphenyldiazeneformaldehyde, phenyldiaZeneacetaldehyde, band valence stabilizers for Mn" and/or Mn" include, but 15 and diphenyldiaZeneacetaldehyde. are not limited to: diphenylcarbazone: 2-phenylcarbazone; N O Valence Stabilizer #32: Examples of diazenediforma dinaphthylcarbazone; and 2-maphthylcarbazone. mides, diaZenediacetamides, bis(diazenediformamides), bis N—O Valence Stabilizer #28: Examples of azo compounds (diaZenediacetamides), poly(diaZenediformamides), and with hydroxyl or carboxy or carbonyl substitution at the poly(diazenediacetamides) (N O Tridentates and N—O ortho- (for aryl) or alpha- or beta- (for alkyl) positions, Bis Hexadentates) that meet the requirements for use as “wide o-(HO—) or alpha- or beta-(HO-)azo compounds, or Poly band valence stabilizers for Mn" and/or Mn" include, but o-(HO—) or alpha- or beta-(HO-)azo compounds) (N O are not limited to: diaZenediformamide, diaZenediacetamide, Bidentates, N OTridentates, N OTetradentates, or N O diphenydiaZenediformamide, tetraphenyldiazenediforma Hexadentates) that meet the requirements for use as “wide 25 mide, diphenyldiaZenediacetamide, and tetraphenyldiazene band' valence stabilizers for Mn" and/or Mn" include, but diacetamide. are not limited to: 2-hydroxyazobenzene 1-(phenylazo)-2- phenol; 2.2'-dihydroxyazobenzene (o.o'-dihydroxyazoben N O Valence Stabilizer #33: Examples of diazenediformic Zene); (2-furan)azobenzene: Direct Blue 2B: 1-(4-nitrophe acids, diaZenediacetic acids, bis(diazenediformic acids), bis nylazo)-2-naphthol; 1-(2-hydroxyphenylazo)-2-naphthol; 30 (diaZenediacetic acids), poly(diazenediformic acids), poly 1-(2-methoxyphenylazo)-2-naphthol; pyridineaZo-2-naph (diazenediacetic acids) and derivatives thereof (N, O Tri thol (PAN); pyridineaZoresorcinol (PAR): 1-phenyl-4-(2-hy dentates and N O Hexadentates) that meet the requirements droxyphenylazo)-5-pyrazolone; 1-phenyl-4-(2-methoxyphe for use as “wide band valence stabilizers for Mn" and/or nylazo)-5-pyrazolone; o-hydroxy-o'-(beta Mn' include, but are not limited to: diazenediformic acid, aminoethylamino)aZobenzene: 2-hydroxy-2'- 35 diaZenediacetic acid, phenyldiazenediformic acid, diphenyl methoxymethyleneoxyazobenzene, methyl red; turquoise diaZenediformic acid, phenyldiazenediacetic acid, and diphe blue (reactive blue); Sunset yellow; amaranth; tartrazine; nyldiazenediacetic acid. Eriochrome Black T. tropeolins: Allura Red; amaranth; Acid Alizarin Violet N. Acid Blue 29; Acid Orange 8, 63, and 74: N O Valence Stabilizer #34: Examples of diazenediformal Acid Red 1, 4, 8, 37, 88,97, 114, 151, and 183: Acid Violet 7: 40 dehydes, diazenediacetaldehydes, bis(diazenediformalde Acid Yellow 25, 29, 34, 42, 76, and 99: Brilliant Black BN: hydes), bis(diazenediacetaldehydes), poly(diaZenediformal Brilliant Crocein; Bordeaux R; Calcion; Chicago Sky Blue: dehydes), and poly(diazenediacetaldehydes) (N O Chromotrope: Cibacron Brilliant Red; Cibacron BrilliantYel Tridentates and N—O Hexadentates) that meet the require low: Crocein Orange; Crystal Scarlet; Calmagite; Direct Blue ments for use as “wide band valence stabilizers for Mn" 71; Direct Red 23, 80, and 81; Direct Violet 51; Direct Yellow 45 and/or Mn" include, but are not limited to: diazenediform 8 and 27: Fast Black; Flavazin; Mordant Blue 9; Mordant aldehyde, diazenediacetaldehyde, diphenyldiazenediformal Brown 1 and 33; Napthol Blue Black: New Coccine; Nitra dehyde, and diphenyldiazenediacetaldehyde. zine Yellow: Nitrosulfonazo III: Orange II: Orange G., OT, N OValence Stabilizer #35: Examples of ortho-hydroxy (or and B: Ponceau.3R and SX; Polar Yellow; 2-oxazolylazoben -carboxy) Substituted formazans, bis(o-hydroxy or -carboxy Zene; and 2-benzoxazolylazobenzene. 50 Substituted formazans), and poly(o-hydroxy or -carboxy Sub N—O Valence Stabilizer #29. Examples of diazeneforma stituted formazans) (N O Bidentates, N—O Tridentates, mides, diaZeneacetamides, bis(diazeneformamides), bis(dia N O Tetradentates, and N—O Hexadentates) that meet the Zeneacetamides), poly(diazeneformamides), and poly(diaz requirements for use as “wide band valence stabilizers for eneacetamides) (N O Bidentates, N. O Tetradentates, and Mn" and/or Mn' include, but are not limited to: 1-(2-hy N—O Hexadentates) that meet the requirements for use as 55 droxyphenyl)-3,5-diphenylformazan: 1-(2-methoxyphenyl)- “wide band' valence stabilizers for Mn" and/or Mn" 3,5-diphenylformazan: 1,5-bis(2-hydroxyphenyl)-3-phenyl include, but are not limited to: diaZeneformamide, diaZene formazan, and 5-bis(2-methoxyphenyl)-3-phenylformazan. acetamide, phenyldiaZeneformamide, diphenyldiaZenefor mamide, phenyldiazeneacetamide, and diphenyldiaZeneac N OValence Stabilizer #36: Examples of ortho-hydroxy (or 60 -carboxy) Substituted azines (including ketazines), bis(o-hy etamide. droxy or carboxy Substituted azines), and poly(o-hydroxy or N—O Valence Stabilizer #30: Examples of diazeneformic carboxy substituted azines) (N-O Bidentates, N—OTriden acids, diaZeneacetic acids, bis(diazeneformic acids), bis(dia tates, N. O Tetradentates, and N—O Hexadentates) that Zeneacetic acids), poly(diaZeneformic acids), poly(diazene meet the requirements for use as “wide band valence stabi acetic acids) and derivatives thereof (N, O Bidentates, 65 lizers for Mn" and/or Mn" include, but are not limited to: N—O Tetradentates, N O Hexadentates) that meet the 2-hydroxy-1-benzalazine; 2-hydroxy-1-naphthalazine; and requirements for use as “wide band valence stabilizers for 2-hydroxy-1-cyclohexanonazine. US 7,789,958 B2 135 136 N-O Valence Stabilizer #37: Examples of Schiff Bases with cyclohexane-1,2-diamine; N.N'-(o-Hydroxyacetophenono) one Imine (C—N) Group and with ortho- or alpha- or beta cyclohexane-1,2-diamine; N,N'-(Salicylaldehydo)-1,2- hydroxy or carboxy or carbonyl substitution (N O Biden diaminobenzene: N,N'-(o-Hydroxynaphthaldehydo)-1,2- tates, N-O Tridentates, N. O Tetradentates, N-O Penta diaminobenzene: N,N'-(o-Hydroxyacetophenono)-1,2- dentates, or N O Hexadentates) that meet the requirements diaminobenzene: N,N'-bis(salicylaldehydo)-1,12 for use as “wide band” valence stabilizers for Mn" and/or diaminododecane (Saldin); N,N'-bis(3- Mn' include, but are not limited to: N-(Salicylaldehydo) methoxysalicylaldehydo)-o-phenyldiamine; N.N'-bis(3,4- isopropylamine; N-(2-Furfuralo)isopropylamine; N-(2- difluorobenzaldehydo)-4,4'-benzidine; and N,N'- Acetylfurano)isopropylamine, N-(2-Hydroxyacetophenono) phenylenebis(3-methoxysalicylidenimine) (V-ph-V). Also isopropylamine; N-(Pyridoxalo)isopropylamine: 10 includes hydrazones with ortho-O substitution. N-(Salicylaldehydo)cyclohexylamine; N-(2-Furfuralo)cy clohexylamine; N-(2-Acetylfurano)cyclohexylamine; N-(2- N-O Valence Stabilizer #39: Examples of Schiff Bases with Hydroxyacetophenono)cyclohexylamine; N-(Pyridoxalo) three Imine (C—N) Groups and with ortho- or alpha- or cyclohexylamine; N-(Salicylaldehydo)aniline; N-(2- beta-hydroxy or carboxy or carbonyl substitution (N O Tet Furfuralo)aniline (Stenhauz salt); N-(2-Acetylfurano) 15 radentates, N—O Pentadentates, or N—OHexadentates) that aniline; N-(2-Hydroxyacetophenono)aniline; meet the requirements for use as “wide band valence stabi N-(Pyridoxalo)aniline; N-(Salicylaldehydo)aminonorbor lizers for Mn" and/or Mn" include, but are not limited to: name: N-(2-Furfuralo)aminonorborname: N-(2-Acetylfurano) N,N',N'-(Salicylaldehydo)tris(2-aminoethyl)amine; N.N. aminonorbornane; N-(2-Hydroxyacetophenono)aminonor N"-(o-Hydroxynaphthaldehydo)tris(2-aminoethyl)amine; bornane; N-(Pyridoxalo)aminonorborname: and N,N',N'-(o-Hydroxyacetophenono)tris(2-aminoethyl) (Salicylaldehydo)anisidine: 2-salicylideneiminobenzothiaz amine. Also includes hydrazones with ortho-O substitution. ole; (Salicylaldehydo)sulfamethazine; and N'-histidine-3- N O Valence Stabilizer #40. Examples of silylaminoalco methoxysalicylidenimine (V-his); N-(o-carboxybenzalde hols (N O Bidentates, N—O Tridentates, N. O Tetraden hydo)-2-aminophenol; N-(salicylaldehydo)isatin: N-(2- tates, and N—O Hexadentates) that meet the requirements for furfuralo)isatin: N-(2-acetylfurano)isatin: N-(pyridoxalo) 25 use as “wide band valence stabilizers for Mn" and/or Mn" isatin: N-(2-hydroxyacetophenono)isatin: hydrofuramide; include, but are not limited to: silatranes. 2-furancarboxaldehyde phenylhydrazone: 2-furancarboxal dehyde 2-pyridyl hydrazone; salicylaldehyde phenylhydra N OValence Stabilizer #41: Examples of hydroxyalkylimi Zone; and salicylaldehyde 2-pyridylhydrazone. Also includes nes (imino alcohols) (N O Bidentates, N O Tridentates, 30 N O Tetradentates, and N—O Hexadentates) that meet the hydrazones with ortho-O substitution. requirements for use as “wide band valence stabilizers for N-O Valence Stabilizer #38: Examples of Schiff Bases with Mn" and/or Mn" include, but are not limited to: 2-hydroxy two Imine (C—N) Groups and with ortho- or alpha- or beta cyclohexylimine, 3-hydroxy-2-iminonorbornane; 2,2'-diimi hydroxy or carboxy or carbonyl substitution (N-O Triden nodicyclohexyl ether, oxamide: 3-imino-1,5-pentanedialde tates, N-O Tetradentates, N O Pentadentates, or N O 35 hyde; iminodiacetic acid; and iminodipropionic acid. Hexadentates) that meet the requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but N O Valence Stabilizer #42: Examples of hydroxyaryl are not limited to: N,N'-(2,5-Furandicarboxaldehydo)diiso amines and hydroxyaryl imines (N O Bidentates, N O propylamine; N,N'-(2,5-Furandicarboxaldehydo)dicyclo Tridentates, N O Tetradentates, and N—O Hexadentates) hexylamine; N.N'-(2,5-Furandicarboxaldehydo)dianiline; 40 that meet the requirements for use as “wide band valence N,N'-(2,5-Furandicarboxaldehydo)di-aminonorbornane; stabilizers for Mn" and/or Mn' include, but are not limited to: 2-aminophenol; 2-aminobenzoic acid (anthranilic acid); N,N'-(o-Hydroxyphthalicdialdehydo)diisopropylamine: 2-aminoanisole; o-phenetidine; o-anisidine, 2-hydroxym N,N'-(o-Hydroxyphthalicdialdehydo)dicyclohexylamine: ethyl)-alpha-aminotoluene, 1-amino-2-naphthol; 2-amino-1- N,N'-(o-Hydroxyphthalicdialdehydo)dianiline; N.N'-(o-Hy naphthol; 2.2'-dicaminomethyl)diphenylketone; isophor droxyphthalicdialdehydo)di-aminonorbornane; N.N'-(o-Hy 45 onediamine; tris-2,4,6-dimethylaminomethyl phenol; di(2- droxyformylcamphoro)diisopropylamine; N,N'-(o-Hy amino)phenyl ether; 1,3-di(2-amino)phenyl-2- droxyformylcamphoro)dicyclohexylamine; N,N'-(o- hydroxypropane; 1,3-di(3-amino)phenyl-2- Hydroxy formylcamphoro)dianiline: N,N'-(o- hydroxypropane; 1,3-di(2-hydroxy)phenyl-2- Hydroxy formylcamphoro)di-aminonorbornane; N.N'-(o- aminopropane; 1,3-di(3-hydroxy)phenyl-2-aminopropane; Hydroxydiacetylbenzeno)diisopropylamine; N,N'-(o- 50 Hydroxydiacetylbenzeno)dicyclohexylamine; N,N'-(o- 2,2'-dihydroxyiminodibenzyl: 2,2'-iminodibenzoic acid; Hydroxydiacetylbenzeno)dianiline: N,N'-(o- 2,2'-dihydroxyiminostilbene; poly(o-phenetidine); poly(o- Hydroxydiacetylbenzeno)di-aminonorbornane; N.N'-(3,6- aminophenol); poly(o-anisidine); and 3-(anilino)propiona Dihydroxy-1,2-cyclohexanono)diisopropylamine; N.N'-(3. mide. 6-Dihydroxy-1,2-cyclohexanono)dicyclohexylamine; N.N'- 55 N O Valence Stabilizer #43: Examples of five-membered (3,6-Dihydroxy-1,2-cyclohexanono)dianiline; N,N'-(3,6- heterocyclic rings containing one, two, three, or four nitrogen Dihydroxy-1,2-cyclohexanono)di-aminonorbornane; N.N'- atoms at least one additional oxygenatom binding site not in (2,5-Diacetylfurano)diisopropylamine; N,N'-(2,5- a ring (N-O Bidentates, N OTridentates, N—O Tetraden Diacetylfurano)dicyclohexylamine; N,N'-(2,5- tates, or N O Hexadentates) that meet the requirements for Diacetylfurano)dianiline; N,N'-(2,5-Diacetylfurano)di 60 use as “wide band valence stabilizers for Mn" and/or Mn" aminonorbornane; N.N'-(Salicylaldehydo)ethylenediamine: include, but are not limited to: 2-hydroxypyrrole: 2-(methyl N,N'-(o-Hydroxynaphthaldehydo)ethylenediamine; N.N'- hydroxy)methylpyrrole; 2.5-(hydroxymethyl)pyrrole; 2.5- (o-Hydroxyacetophenono)ethylenediamine; N.N'-(Salicylal (methylhydroxymethyl)pyrrole; imidazoline-2-one (2-hy dehydo)trimethylenediamine; N.N'-(o-Hydroxynaphthalde droxyimidazole); 2-hydroxythiazoline; hydo)trimethylenediamine: N,N'-(o-Hydroxyacetophenono) 65 2-hydroxybenzimidazole: 2-hydroxybenzothiazole; 2-hy trimethylenediamine; N,N'-(Salicylaldehydo)cyclohexane droxybenzoxazole, 2-hydantoin; di-2-pyridylglyoxal (2,2'- 1.2-diamine; N,N'-(o-Hydroxynaphthaldehydo) pyridil); bis((1-pyrazolyl)methane)ether; bis(2-(1-pyrazolyl) US 7,789,958 B2 137 138 ethane)ether; bis(benzimidazolylmethane)ether; bis least one additional nitrogen atom binding site not in a ring (benzimidazolylethane)ether; tris(imidazolyl)methanol; tris (N—O Bidentates, N O Tridentates, N. O Tetradentates, (imidazolylmethane)methanol; N-hydroxymethyl-N,N- or N O Hexadentates) that meet the requirements for use as (benzimidazolylmethane)amine; N-(2-hydroxyethyl)-N,N- “wide band valence stabilizers for Mn" and/or Mn" (benzimidazolylmethane)amine; N,N'-di include, but are not limited to: 2-aminopyran; 2,6-diaminopy (benzimidazolylmethane)-1,3-diamino-2-hydroxypropane; ran; 2-aminomethylpyran; 2,6-di(aminomethyl)pyran; and N.N.N',N'-tetrakis(benzimidazolylmethane)-1,3-diamino-2- 2-aminobenzopyran. hydroxypropane; bis(N.N-((4-imidazolyl)methane)-2-ami noethane)ether, 4-carboxybenzotriazole; antipyrine: 4-ami N O Valence Stabilizer #47: Examples of five-membered noantipyrine (aap); hydantoin; aminoalkylhydantoins; 2.5- 10 heterocyclic rings containing one, two, three, or four nitrogen oxazolidinedione; benzyldibenzoyltriazole (bdbt): atoms at least one additional oxygen atom binding site in a 5-hydroxymethylimidazole; dicarboxyalkylbenzotriazoles; separate ring (N-O Bidentates, N—O Tridentates, N—O bis(hydroxyphenyl)aminotriazoles; pyrrole-2-carboxalde Tetradentates) that meet the requirements for use as “wide hyde; (oxopyrrolidinylalkyl)triazoles; alkoxybenzotriazoles: band' valence stabilizers for Mn, and/or Mn" include, but aryloxybenzotriazoles; 3-salicylamido-4,5-dihydro-1,2,4- 15 are not limited to: 2-(2-furan)pyrrole; 2,5-di(2-furan)pyrrole; triazole, 5-(alkoxy)benzotriazole; (polyoxyalkylene)oxazo 2-(2-pyran)pyrrole; 2,5-di(2-pyran)pyrrole; 2,5-di(2-pyr lidines: 1-(dialkylaminomethyl)-5-carboxyalkylbenzotriaz role)furan; and 2,6-di(2-pyrrole)pyran. ole: 1-(2-hydroxyethyl)imidazoline: 1-acetoxyimidazole; N O Valence Stabilizer #48: Examples of six-membered 1-acetylimidazole; benzotriazolecarboxylic acid; poly(oxy heterocyclic rings containing one, two, three, or four nitrogen alkylated)pyrazoles; poly(oxyalkylated)thiadiazoles; 1,2,4- atoms at least one additional oxygen atom binding site in a triazole-3-carboxylic acid; 5-hydroxypyrazole; 3-phenyl-1, separate ring (N-O Bidentates, N—O Tridentates, N—O 2,4-triazol-5-one (ptr); 1-acetylbenzimidazole, 1-(acetoxy) Tetradentates) that meet the requirements for use as “wide ethylbenzimidazole; creatinine; indole-2-carboxylic acid; band' valence stabilizers for Mn, and/or Mn" include, but pyrrole-2-carboxylic acid; imidazole-2-carboxylic acid; are not limited to: 2-(2-furan)pyridine; 2,6-di(2-furan)pyri pyrazole-2-carboxylic acid; and 1,1'-oxalyldiimidazole. 25 dine: 2-(2-pyran)pyridine; 2,6-di(2-pyran)pyridine; 2,5-di(2- N—O Valence Stabilizer #44: Examples of six-membered pyridyl)furan; 2,6-di(2-pyridyl)pyran; and drometrizole. heterocyclic rings containing one, two, three, or four nitrogen N O Valence Stabilizer #49: Examples of two-, three atoms at least one additional oxygenatom binding site not in four-, six-, eight-, and ten-membered macrocyclics, macro a ring (N O Bidentates, N OTridentates, N. O Tetraden 30 bicyclics, and macropolycyclics (including catapinands, tates, or N O Hexadentates) that meet the requirements for cryptands, cyclidenes, and sepulchrates) wherein all binding use as “wide band” valence stabilizers for Mn' and/or Mn" sites are composed of nitrogen (usually amine or imine include, but are not limited to: 4-aminomethyl-3-py groups) or oxygen (usually hydroxy, carboxy, or carbonyl ridinemethanol (including pyridoxamine); 2-hydroxypyri groups) and are not contained in component heterocyclic dine: 2-(methylhydroxy)methylpyridine: 2-(2-(methylhy 35 rings (N O Bidentates, N—O Tridentates, N. O Tetraden droxy)ethyl)pyridine; 2,6-(hydroxymethyl)pyridine; 2,6- tates, and N—O Hexadentates) that meet the requirements for (methylhydroxymethyl)pyridine; 2-hydroxypyrimidine; use as “wide band valence stabilizers for Mn" and/or Mn" 2-dihydroxymethylpyrimidine: 2-hydroxyquinoline; 8-hy include, but are not limited to: azaoxacyclobutane (4 droxyquinoline (oxine); 8-methylhydroxyquinoline, 2-hy aneNO); azaoxacyclopentane (5aneNO), azaoxacyclohex droxyquinazoline; orotic acid (1.2.3,6-tetrahydro-2,6-dioxo 40 ane (6aneNO); azaoxacycloheptane (7aneNO); azaoxacy 4-pyrimidinecarboxylic acid) (6-uracilcarboxylic acid); clooctane (8aneNO); azaoxacyclobutene (4 eneNO); 1-methylpyrimidine-2-one: uracil; 6-hydroxypurine; bis(N, aZaoxacyclopentene (5eneNO); aZaoxacyclohexene (6 N,N',N'-tetra(2-(2-pyridyl)ethane)aminomethane)ether; bis eneNO); azaoxacycloheptene (7eneNO); azaoxacy (N.N.N',N'-tetra(2-(2-pyridyl)ethane)aminoethane)ether; clooctene (8 eneNO); azaoxacyclobutadiene (4dieneNO); quinazol-4-One; quinazol-2-one; 5-azathymine; 2-hydroxy 45 aZaoxacyclopentadiene (5dieneNO); azaoxacyclohexadi benzimidazole (2-hbZ); guanine; 1,3,5-triazin-6-one; 6-hy ene (6dieneNO); azaoxacycloheptadiene (7dieneNO); droxy-1,3,5-triazine; 4,6-dihydroxy-1,3,5-triazine; triazine aZaoxacyclooctadiene (8dieneNO); diazaoxacyclohexane carboxylic acids: 2,3-dihydroxypyridine; thiomorpholin-3- (6aneCN); diazaoxacycloheptane (7aneON); diazaox one; hydroxytetrahydropyrimidines; 2-piperazinones; 2-pip acyclooctane (8aneON); diazaoxacyclononane (9 eridinones; dilituric acid; actinoquinol; caffeine; citrazinic 50 aneCN); diazaoxacyclodecane (10aneON); diazaoxacy acid; picolinic acid; 2-quinolol; 2,6-dimethoxypyridine; qui cloundecane (11 laneCN); diazaoxacyclododecane (12 noxaline-2-carboxylic acid; flucytosine; hypoxanthine; hex aneCN); diazaoxacyclohexene (6ene(ON); amethylolmelamine; hydroorotic acid; isoorotic acid; Xan diazaoxacycloheptene (7eneCN); diazaoxacyclooctene thine; leucopterin: nitroorotic acid; 8-azaguanine; and (8eneCN); diazaoxacyclononene (9eneCN); diazaox cyanuric acid. 55 acyclodecene (10 eneCN); diazaoxacycloundecene (11 eneCN); diazaoxacyclododecene (12eneCN); diazadiox N—O Valence Stabilizer #45: Examples of five-membered acyclooctane (8 laneON); diazadioxacyclononane (9 heterocyclic rings containing one or two oxygen atoms at aneCN); diaZadioxacyclodecane (10aneCN); least one additional nitrogen atom binding site not in a ring diazadioxacycloundecane (11aneCN); diazadioxacy (N—O Bidentates, N O Tridentates, N—O Tetradentates, 60 clododecane (12aneON); diazadioxacyclotridecane (13 or N O Hexadentates) that meet the requirements for use as aneCN); diazadioxacyclotetradecane (14aneCN); “wide band valence stabilizers for Mn" and/or Mn" diazadioxacyclopentadecane (15aneON); diazadioxacy include, but are not limited to: 2-aminofuran; 2,5-diaminofu clohexadecane (16aneON); diazadioxacycloheptadecane ran; 2-aminomethylfuran; 2,5-di(aminomethyl)furan, 2-ami (17aneON); diaZadioxacyclooctadecane (18 laneCN); nobenzofuran; and 2-amino-1,3-dioxolane. 65 diazadioxacyclononadecane (19aneON); diazadioxacyc N—O Valence Stabilizer #46: Examples of six-membered loeicosane (20aneON); diazadioxacyclooctadiene (8 heterocyclic rings containing one or two oxygen atoms at dieneON); diazadioxacyclononadiene (9dieneON); US 7,789,958 B2 139 140 diazadioxacyclodecadiene (10dieneON); diazadioxacy Tridentates, S O Tetradentates) that meet the requirements cloundecadiene (11 dieneON); diazadioxacyclododecadi for use as “wide band valence stabilizers for Mn" and/or ene (12dieneON); diazadioxacyclotridecadiene (13 Mn" include, but are not limited to: 2-acetothioacetamide, dieneON); diazadioxacyclotetradecadiene (14 2-thioacetoacetamide, N-phenyl-2-acetothioacetamide, dieneON); diazadioxacyclopentadecadiene (15 N-pentafluorophenyl-2-acetothioacetamide, N-benzyl-2-ac dieneON); diazadioxacyclohexadecadiene (16) etothioacetamide, N-cyclohexyl-2-acetothioacetamide, dieneON); diazadioxacycloheptadecadiene (17) N-norbornyl-2-acetothioacetamide, N-phenyl-2-benzothio dieneON); diazadioxacyclooctadecadiene (18) acetamide, N-pentafluorophenyl-2-pentafluorobenzothioac dieneON); diazadioxacyclononadecadiene (19) etamide, and N-cyclohexyl-2-cyclohexothioacetamide. 10 dieneON); and diazadioxacycloeicosadiene (20 S O Valence Stabilizer #4: Examples of dithiodicarbonic dieneON). diamides, bis(dithiodicarbonic diamides), and poly(dithiodi N—OValence Stabilizer #50: Examples of four-, six-, eight-, carbonic diamides) (S O Bidentates, S O Tridentates, or ten-membered macrocyclics, macrobicyclics, and S O Tetradentates) that meet the requirements for use as macropolycyclics (including catapinands, cryptands, cyclid 15 “wide band' valence stabilizers for Mn" and/or Mn" enes, and sepulchrates) wherein all binding sites are com include, but are not limited to: dithiodicarbonic diamide: posed of nitrogen or oxygen and are contained in component N-phenyldithiodicarbonic diamide: N-pentafluorophe heterocyclic rings (N O Bidentates, N O Tridentates, nyldithiodicarbonic diamide: N-benzyldithiodicarbonic dia N—O Tetradentates, or N—O Hexadentates) that meet the mide: N-cyclohexyldithiodicarbonic diamide; N-nor requirements for use as “wide band valence stabilizers for Mn" and/or Mn" include, but are not limited to: dipyran bornyldithiodicarbonic diamide: N,N'- dipyridines; difurandipyrroles; tripyrantripyridines; tri diphenyldithiodicarbonic diamide: N,N'- furantripyrroles; tetrapyrantetrapyridines; and tetrafurantet dipentafluorophenyldithiodicarbonic diamide: N,N'- rapyrroles. dibenzyldithiodicarbonic diamide: N,N'- dicyclohexyldithiodicarbonic diamide; and N,N'- N—OValence Stabilizer #51: Examples of four-, six-, eight-, 25 dinorbornyldithiodicarbonic diamide. or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclid S O Valence Stabilizer #5. Examples of monothiohypo enes, and sepulchrates) wherein all binding sites are com phosphoric acids, bis(monothiohypophosphoric acids), poly posed of nitrogen or oxygen and are contained in a combina (monothiohypophosphoric acids), and derivatives thereof tion of heterocyclic rings and amine, imine, hydroxy, 30 (S O Bidentates. S- O Tridentates, S O Tetradentates) carboxy, or carbonyl groups (N O Bidentates, N. O Tri that meet the requirements for use as “wide band valence dentates, N. O Tetradentates, or N—O Hexadentates) that stabilizers for Mn" and/or Mn" include, but are not limited meet the requirements for use as “wide band valence stabi to: monothiohypophosphoric acid, methylmonothiohypo lizers for Mn" and/or Mn" include, but are not limited to: phosphoric acid, isopropylimonothiohypophosphoric acid, aZaoxatetraphyrins; diazadioxatetraphyrins; azaoxahexaphy 35 tert-butylmonothiohypophosphoric acid, phenylmonothio rins; diazadioxahexaphyrins; and triaZatrioxahexaphyrins. hypophosphoric acid, pentafluorophenylmonothiohy pophosphoric acid, benzylmonothiohypophosphoric acid, S O Valence Stabilizer #1: Examples of 1.3-monothioke cyclohexylmonothiohypophosphoric acid, norbornylmono tones (monothio-beta-ketonates), 1.3.5-monothioketones, thiohypophosphoric acid, dimethylmonothiohypophospho 1,3,5-dithioketones, bis(1.3-monothioketones), and poly(1, 40 ric acid, diisopropylimonothiohypophosphoric acid, di-tert 3-monothioketones) (S-O Bidentates, S O Tridentates, butylmonothiohypophosphoric acid, S O Tetradentates) that meet the requirements for use as diphenylmonothiohypophosphoric acid, di-pentafluorophe “wide band valence stabilizers for Mn" and/or Mn" nylmonothiohypophosphoric acid, dibenzylmonothiohypo include, but are not limited to: hexafluoropenta-2-thione-4- phosphoric acid, dicyclohexylmonothiohypophosphoric ketone; 1,3-diphenyl-1,3-propana-1-thione-3-ketone; ben 45 Zoylthiopinacolone; cyclohexoylthiocyclohexoylmethane; acid, and dinorbornylmonothiohypophosphoric acid. diphenylpentanedithionate; tetramethylnonanedithionate; S O Valence Stabilizer #6: Examples of monothiohypo hexafluoroheptanedithionate; trifluoroheptanedithionate; phosphoramides, bis(monothiohypophosphoramides), and 1-(2-thienyl)-butan-1-thione-3-ketone, 1- (2-naphthyl)-bu poly(monothiohypophosphoramides) (S-O Bidentates, tan-1-thione-3-ketone, and trifluoroacetylthiocamphor. 50 S OTridentates, S. O Tetradentates) that meet the require ments for use as “wide band” valence stabilizers for Mn' S O Valence Stabilizer #2: Examples of thiomalonamides and/or Mn" include, but are not limited to: monothiohypo (thiomalonodiamides), bis(thiomalonamides), and polythi phosphoramide, N-methylmonothiohypophosphoramide, omalonamides (S O Bidentates, S O Tridentates. S- O N-isopropylimonothiohypophosphoramide, N-tert-butyl Tetradentates) that meet the requirements for use as “wide 55 monothiohypophosphoramide, N-phenylmonothiohypo band valence stabilizers for Mn" and/or Mn" include, but phosphoramide, N-pentafluorophenylmonothiohy are not limited to: thiomalonamide, N-phenylthiomalona mide, N-benzylthiomalonamide, N-pentafluorophenylthi pophosphoramide, N-benzylmonothiohypophosphoramide, omalonamide, N-cyclohexylthiomalonamide, N-nor N-cyclohexylmonothiohypophosphoramide, N-norbornyl bornylthiomalonamide, N,N'-diphenylthiomalonamide, monothiohypophosphoramide, N.N"-dimethylmonothiohy 60 pophosphoramide, N.N"-diisopropylimonothiohypophos N,N'-dibenzylthiomalonamide, N,N'-dipentafluorophe phoramide, N,N'-di-tert nylthiomalonamide, N,N'-dicyclohexylthiomalonamide, and butylmonothiohypophosphoramide, N,N"- N,N'-norbornylthiomalonamide. diphenylmonothiohypophosphoramide, N,N'-di S O Valence Stabilizer #3: Examples of 2-thioacylaceta pentafluorophenylmonothiohypophosphoramide, N,N"- mides, 2-acylthioacetamides, bis(2-thioacylacetamides), bis 65 dibenzylmonothiohypophosphoramide, N,N"- (2acylthioacetamides), poly(2-thioacylacetamides), and poly dicyclohexylmonothiohypophosphoramide, and N.N"- (2-Acylthioacetamides) (S O Bidentates, S- O dinorbornylmonothiohypophosphoramide. US 7,789,958 B2 141 142 S O Valence Stabilizer #7: Examples of monothioimido dicyclohexylmonothiodiphosphoramide, and N,N'-dinor diphosphoric acids, monothiohydrazidodiphosphoric acids, bornylmonothiodiphosphoramide. bis(monothioimidodiphosphoric acids), bis(monothiohy S O Valence Stabilizer #10: Examples of monothiodiphos drazidodiphosphoric acids), poly(monothioimidodiphospho phoric acids, bis(monothiodiphosphoric acids), poly(mono ric acids), poly(monothiohydrazidodiphosphoric acids), and 5 thiodiphosphoric acids), and derivatives thereof (S- O derivatives thereof (S O Bidentates. S- O Tridentates, Bidentates, S OTridentates. S- O Tetradentates) that meet S O Tetradentates) that meet the requirements for use as the requirements for use as “wide band valence stabilizers “wide band valence stabilizers for Mn" and/or Mn" for Mn" and/or Mn' include, but are not limited to: mono include, but are not limited to: monothioimidodiphosphoric thiodiphosphoric acid, methylmonothiodiphosphoric acid, acid, methylmonothioimidodiphosphoric acid, isopropyl 10 isopropylimonothiodiphosphoric acid, tert-butylmonothio monothioimidodiphosphoric acid, tert-butylmonothioimido diphosphoric acid, phenylmonothiodiphosphoric acid, pen diphosphoric acid, phenylmonothioimidodiphosphoric acid, tafluorophenylmonothiodiphosphoric acid, benzylmonothio pentafluorophenylmonothioimidodiphosphoric acid, benzyl diphosphoric acid, cyclohexylmonothiodiphosphoric acid, monothioimidodiphosphoric acid, cyclohexylmonothioimi norbornylmonothiodiphosphoric acid, dimethylmonothio dodiphosphoric acid, norbornylmonothioimidodiphosphoric 15 acid, dimethylmonothioimidodiphosphoric acid, diisopropy diphosphoric acid, diisopropylimonothiodiphosphoric acid, lmonothioimidodiphosphoric acid, di-tert-butylmonothio di-tert-butylmonothiodiphosphoric acid, diphenylmonothio imidodiphosphoric acid, diphenylmonothioimidodiphos diphosphoric acid, di-pentafluorophenylmonothio phoric acid, diphosphoric acid, dibenzylmonothiodiphosphoric acid, di-pentafluorophenylmonothioimidodiphosphoric acid, dicyclohexylmonothiodiphosphoric acid, and dinorbornyl dibenzylmonothioimidodiphosphoric acid, dicyclohexyl monothiodiphosphoric acid. monothioimidodiphosphoric acid, and dinorbornylmono S OValence Stabilizer #11: Examples of monothiocarbam thioimidodiphosphoric acid. ates, bis(monothiocarbamates), and poly(monothiocarbam S O Valence Stabilizer #8: Examples of monothioimido ates) (including N-hydroxymonothiocarbamates and N-mer diphosphoramides, monothiohydrazidodiphosphoramides, 25 captomonothiocarbamates) (S- O Bidentates. S- O Tridentates, and S- O Tetradentates) that meet the require bis(monothioimidodiphosphoramides), bis(monothiohy ments for use as “wide band” valence stabilizers for Mn' drazidodiphosphoramides), poly(monothioimidodiphos and/or Mn" include, but are not limited to: dimethylmono phoramides), and poly(monothiohydrazidodiphosphora thiocarbamate (dmmtc); di(trifluorodimethyl)monothiocar mides) (S-O Bidentates. S- O Tridentates. S- O Tetradentates) that meet the requirements for use as “wide 30 bamate; diethylmonothiocarbamate (demtc); dipropylimono band valence stabilizers for Mn" and/or Mn" include, but thiocarbamate; diisopropylimonothiocarbamate; are not limited to: monothioimidodiphosphoramide, N-me dibutylmonothiocarbamate; ditertbutylmonothiocarbamate: thylmonothioimidodiphosphoramide, N-isopropylimono dicyanamidomonothiocarbamate; diphenylmonothiocar thioimidodiphosphoramide, N-tert-butylmonothioimido bamate; di(pentafluorophenyl)monothiocarbamate: diben diphosphoramide, 35 Zylimonothiocarbamate; dinaphthylmonothiocarbamate; N-phenylmonothioimidodiphosphoramide, N-pentafluo dicyclohexylmonothiocarbamate; dinorbornylmonothiocar rophenylmonothioimidodiphosphoramide, N-benzylmono bamate; diadamantylmonothiocarbamate; pyrrolidinomono thioimidodiphosphoramide, N-cyclohexylmonothioimido thiocarbamate (pyrmtc); piperidinomonothiocarbamate (pip diphosphoramide, mtc); morpholinomonothiocarbamate (mormtc); N-norbornylmonothioimidodiphosphoramide, N.N"-dim 40 thiamorpholinomonothiocarbamate; 3-pyrrolinomonothio ethylmonothioimidodiphosphoramide, N.N"-diisopropyl carbamate; pyrrolomonothiocarbamate; oxazolomonothio monothioimidodiphosphoramide, N,N'-di-tert-butylmono carbamate; isoxazolomonothiocarbamate; thiazolomono thioimidodiphosphoramide, N,N'- thiocarbamate; isothiazolomonothiocarbamate; diphenylmonothioimidodiphosphoramide, N,N'-di indolomonothiocarbamate; carbazolomonothiocarbamate; pentafluorophenylmonothioimidodiphosphoramide, N.N"- 45 pyrazolinomonothiocarbamate; imidazolinomonothiocar dibenzylmonothioimidodiphosphoramide, N,N'- bamate; pyrazolomonothiocarbamate; imidazolomonothio dicyclohexylmonothioimidodiphosphoramide, and N.N"- carbamate; indazolomonothiocarbamate; and triazolomono dinorbornylmonothioimidodiphosphoramide. thiocarbamate. Miscellaneous Valence Stabilizer #1: Examples of hydroxo S O Valence Stabilizer #9: Examples of monothiodiphos 50 and OXO functionalities that meet the requirements for use as phoramides, bis(monothiodiphosphoramides), and poly “wide band' valence stabilizers for Mn" and/or Mn" (monothiodiphosphoramides) (S O Bidentates, S O Tri include, but are not limited to: water (H2O); dioxygen (O); dentates. S- O Tetradentates) that meet the requirements for oxide (O); hydroxide (OH); peroxo groups (O); and use as “wide band' valence stabilizers for Mn, and/or Mn" Superoxo groups (O). include, but are not limited to: monothiodiphosphoramide, 55 N-methylmonothiodiphosphoramide, N-isopropylimonothio As with the inorganic Valence stabilizers, crosses between diphosphoramide, N-tert-butylmonothiodiphosphoramide, two or more organic stabilizers can be used. For example, in some instances it may be desirable to form a valence stabilizer N-phenylmonothiodiphosphoramide, N-pentafluorophenyl out of a nitrogen-containing heterocyclic and an amine monothiodiphosphoramide, N-benzylmonothiodiphos ligand. During the synthesis process, both of these materials phoramide, N-cyclohexylmonothiodiphosphoramide, N-nor 60 bornylmonothiodiphosphoramide, N,N'- will complex with the MnIII or MnIV ion to produce a mixed dimethylmonothiodiphosphoramide, N,N'- nitrogen heterocyclic/amine Valence stabilizer compound diisopropylimonothiodiphosphoramide, N,N'-di-tert from the pigment solution. butylmonothiodiphosphoramide, N,N'- 3c) Narrow Band Inorganic Valence Stabilizers diphenylmonothiodiphosphoramide, N,N'-di 65 Additional Valence stabilizers can be used in conjunction pentafluorophenylmonothiodiphosphoramide, N,N'- with the MnIII and MnIV ions for corrosion protection. How dibenzylmonothiodiphosphoramide, N,N'- ever, these less typical stabilizers suffer from disadvantages US 7,789,958 B2 143 144 that make their selection over the previously mentioned wide thereby leads to lower corrosion protection. Nonetheless, band valence stabilizers less desirable. For this reason, we these complexes also demonstrate Some corrosion inhibiting term them “narrow band valence stabilizers because of their activity. The additional ions that can be included within the limited applications. Narrow band stabilizers exhibit some central cavity of the heteropolymetallates described above limitation in their use when compared to wide band stabiliz- 5 depend upon the size of the central cavity, which in turn ers. Narrow band inorganic stabilizers may be toxic or may depends upon the specific chemistry exhibited by an inor complex MnIII or MnIV only with difficulty. These narrow ganic valence stabilizer (e.g., molybdate, tungstate, perio band stabilizers include, but are not limited to, bismuthates, date, etc.) In general, these additional ions must also be small germanates, arsenates, and carbonates. For example, Valence so as to ensure the stability of the formed MnIII- or MnIV stabilizers using arsenate are less desirable because their 10 Valence stabilized complex. Examples of Small additional inherent toxicity is very large (greater than PbV or CrVI), ions include, but are not limited to: B", Al", Si", P., Ti", although they may be very effective at inhibiting corrosion V+5, V+, Cr'6, Cr's, Mn+2, Fe+3, Fe+2, Cots, Co-2, Nit-2, when used with Mn(II. Arsenates could be used as Mn(II Ni", Ni, Cut, Cu, Zn, Ga, Ge", As", As", Zr", valence stabilizers in situations where the toxicity of the and Ce". pigment is not a factor in its use. 15 Water-soluble precursors for these materials are desirable. Modifications of wide band inorganic valence stabilizers Typically, the free acids (e.g., silicomolybdic acid, phospho can result in a complex with reduced corrosion inhibition. tungstic acid, borotungstic acid, etc.) offer the most water The central cavity of the heteropolymetallates can contain soluble precursors for these materials. ions in addition to the desired Mn or MnV ion. For example, the use of silicomolybdates, phosphomolybdates, 20 3d) Narrow Band Organic Valence Stabilizers silicotungstates, and phosphotungStates is possible. In these Narrow band organic Valence stabilizers include those gen MnIII- or MnIV-valence stabilizer complexes, Si" or Pt eral classes of chemical compounds that result in MiniTI- or ions also occupy the central cavity of the complex with the MnIV-valence stabilizer compounds that are either less MnIII or MnV ion. The inclusion of additional ions in the stable, more soluble in water, or more toxic than the wide central cavity reduces the stability of the complex, and band organic stabilizers.

TABLE 5 Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation NValence 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 metalion. 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 metalion. 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. NValence 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 hydrocarbonfring 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 metalion. 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. NValence 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 metalion. 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 metalion. This ligand and/or attached, uncoordinating hydrocarbon rings may or may not have halogen or polarizing or water insolubilizing groups attached. NValence 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 hydrocarbonfring 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 metalion. 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 US 7,789,958 B2 145 146

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Tridentates, N N Tetradentates, or N N or polarizing or water-insolubilizing groups Hexadentates) attached. NValence 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 metalion. 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 metalion. This ligand and/or attached, uncoordinating hydrocarbon rings may or may not have halogen or polarizing or water insolubilizing groups attached. NValence Stabilizer #6: N(SiR), RN(SiR), or R'R''N(SiR) for Sillylamines and SilaZanes, including silylamines; and RR"Si-NR (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 Seatoms. NValence 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 rom 0 to 40, optionally having halogen or Hexadentates) polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence 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) rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence 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 unctional 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 Patoms. NValence Stabilizer #10: (NH-)PR"( NRR')( OR") for Phosphonamidimidic Acid, phosphonamidimidic acid and (NH-)PR"(—NRR") (—SR") Phosphonamidimidothioic Acid, orphosphonamidimidothioic 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. N. water-insolubilizing solubilizing groups Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or Patoms. NValence 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. —CHs), 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 Patoms. NValence Stabilizer #12: R-NH-N=R', where R and R' represent Hor Hydrazones, Bis(hydrazones), and any organic functional group wherein the Poly(hydrazones) (NMonodentates, 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 Patoms. US 7,789,958 B2 147 148

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation NValence 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 Hor 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) (NMonodentates, N N water-insolubilizing solubilizing groups Bidentates, or N N N Tridentates) attached. (Not including ortho-chelate Substituted arylazo compounds, and alpha- or beta-substituted alkyl azo compounds.) Ligand can also contain nonbinding N, O, S, or P atOnS. NValence 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-NBidentates, N N or polarizing or water 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 Patoms. NValence 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 Patoms. NValence Stabilizer #16: RRC=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-NBidentates, N N optionally having halogen or polarizing or 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 Patoms. NValence 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, (NMonodentates) thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido Substitution.) Ligand can also contain nonbinding N, O, S, or Patoms. NValence Stabilizer #18: Isocyanides, cyanamides, and related ligands Isocyanide and Cyanamide and related where the nitrogen atom is directly complexed ligands (NMonodentates) to the high valence metalion. NValence 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 metalion. NValence Stabilizer #20: R—CN, R—(CN), R—(CN), 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. NValence Stabilizer #21: AZide (—N) ligands bound directly to the high Azide ligands (NMonodentates, or N N valence metalion. Also includes organoaZide Bidentates) derivatives (R—N), triazenido compounds (R—N -R), phosphonyl azides (R—PO2H- N3), phosphoryl azides (O-POH- N3), and sulfonyl azides (R-SO-N) 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 SValence Stabilizer #1: SH2, SHR, SR2, where R represents H or any Monothioethers (S Monodentates) wherein organic functional group wherein the number of US 7,789,958 B2 149 150

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 Seatoms SValence 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 Seatoms. SValence 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 Seatoms. SValence 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 rom 0 to 35, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, P., O, S, or Seatoms. SValence 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 unctional 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 Seatoms. SValence 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 rom 0 to 35, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, P., O, S, or Seatoms. SValence 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 Seatoms. This 5-membered ring and/or attached , uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. SValence 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 unction 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 hey do not coordinate with the stabilized, high Bidentates) valence metalion. Ring can also contain O, N, C , AS, or Seatoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. SValence 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 Seatoms. This 5-membered ring(s) and/or attached, uncoordinating rings and/or S containing Substituent(s) may or may not have US 7,789,958 B2 151 152

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation halogen or polarizing or water insolubilizing solubilizing groups attached. SValence 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 Seatoms. 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. SValence 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-S ring systems bound to the S-containing 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. SValence 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-S ring systems bound to the S-containing 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. SValence 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 metalion. This ligand andfor wherein all Binding Sites are composed of attached, uncoordinating hydrocarbons frings 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) SValence 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. SValence 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 metalion. 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 US 7,789,958 B2 153 154

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Tridentates, S-S Tetradentates, or S-S valence metalion. This ligand and/or attached, Hexadentates) uncoordinating hydrocarbon rings may or may not have halogen or polarizing or water insolubilizing groups attached. SValence 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. SValence 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 metalion. 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 metalion. This ligand and/or attached, Hexadentates) uncoordinating hydrocarbon rings may or may not have halogen or polarizing or water insolubilizing groups attached. SValence Stabilizer #18: RR N C(=S) NR" C(=S)-NR"R" for Dithiobiurets (Dithioimidodicarbonic dithiobiurets, and RR' N C(=S)- NR" NH C(=S) NR"R" Diamides), Dithioisobiurets, Dithiobiureas, or dithiobiureas, where R, R', Trithiotriurets, Trithiotriureas, R", R", and R" represent H, NH, 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 Patoms. SValence Stabilizer #19: RR' N C(=S)- NR" C(=S) R" where R, R', R", Thioacylthioureas, Thioaroylthioureas, and R" represent H, NH, or any organic Bis(thioacylthioureas), unctional 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.–S insolubilizing solubilizing groups attached. Tridentates, S-S Tetradentates) Ligand can also contain nonbinding N, O, S, or Patoms. SValence 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 isulfides), and Poly(dithioacyl disulfides) wherein the number of carbon atoms ranges (S–S Bidentates, S-S Tridentates, S-S rom 0 to 40, optionally having halogen or Tetradentates) polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence 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 iamides) (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 Patoms. SValence Stabilizer #22: R-S-C(=S)—S–S C(=S)—S-R' for Hexathio-, Pentathio-, and hexathioperoxydicarbonic acids, R-O-C(=S)—S—S—C(=S)—S—R' Tetrathioperoxydicarbonic Acids, 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, NH2 or 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 Patoms. US 7,789,958 B2 155 156

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation SValence Stabilizer #23: Dithioperoxydiphosphoramide, where R, R', R", R", Bis(dithioperoxyphosphoramide), and R", R", R", and R" represent H, NH, or 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 Patoms. SValence Stabilizer #24: (R-O-)(R'—O-)P(=S)—S-S-P(=S)(-O-R") (—O—R"); Dithioperoxydiphosphoric Acids, (R-O-)(R'—S—)P(=S)-S-S-P(—S) (—S—R") (—O—R"); Bis(dithioperoxyphosphoric Acids), or (R-S )(R'—S—)P(—S)-S-S-P(=S)(—S—R") (—S—R"), Poly(dithioperoxydiphosphoric Acids), and where R, R', R", R", R", R", R", derivatives thereof (S–S Bidentates, S-S and R" represent H, NH2 or 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 SValence Stabilizer #25: Dithioimidodiphosphonic Acids, Dithiohydrazidodiphosphonic Acids, Bis(dithioimidodiphosphonic acids), Bis(dithiohydrazidodiphosphonic acids), acids, and - NH-NH Poly(dithioimidodiphosphonic acids), derivatives for dithiohydrazidodiphosphonic Poly(dithiohydrazidodiphosphonic acids), acids, where R, R', R", and R" represent H, and derivatives thereof (S–S Bidentates, S.–S NH2 or any organic functional group wherein Tridentates, and S-S 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 Patoms. SValence Stabilizer #26: (RR' N )(R" )P(=S) NH P(=S)( R") ( N R"R") Dithioimidodiphosphonamides, for dithioimidophosphonamides, and Dithiohydrazidodiphosphonamides, (RR' N )(R" )P(=S) NH NH P(=S)( R")( N R"R") Bis(dithioimidodiphosphonamides), for dithiohydrazidodiphosphonamides, Bis(dithiohydrazidodiphosphonamides), Poly(dithioimidodiphosphonamides), and R", and R" represent H, NH2 or 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 Patoms. SValence Stabilizer #27: (RR' N )(R" )P(=S)–S P(=S)(-R")( N R"R"), Dithiodiphosphonamides, or (RR' N )(R" )P(=S)- O P(=S)( R") ( N R"R"), Bis(dithiophosphonamides), and where R, R', R", R", R", Poly(dithiodiphosphonamides) (S–S and R" represent H, NH, or 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 Patoms. SValence Stabilizer #28: (R-O-)(R'—)P(—S)—O—P(=S)(—R")(-O-R"); Dithiodiphosphonic Acids, (R-O-)(R'—)P(—S)—S—P(—S) (—R")(-O-R"); Bis(dithioiphosphonic Acids), (R-S–)(R'—)P(=S)—O—P(—S) (—R")(—S—R"); Poly(dithiodiphosphonic Acids), and or (R-S )(R'—)P(=S)—S—P(=S)(—R") (—S—R"); derivatives thereof (S–S Bidentates, S-S where R, R', R", Tridentates, S-S Tetradentates) 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. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #29: (RR' N )(R" )P(=S)-S-S P(=S)(-R") ( N R"R"), Dithioperoxydiphosphonamide, where R, R', R", R", R", and R" Bis(dithioperoxyphosphonamide), and represent H, NH2 or 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 Patoms. SValence 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"), US 7,789,958 B2 157 158

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Bis(dithioperoxyphosphonic Acids), where R, R', R", and R" represent H, NH2 or 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 Patoms. SValence Stabilizer #31: Dithiophosphonic (O-)PR(-S-R')(-S R") or (S-)PR(-S R')(-O-R"), Acids (Phosphonodithioic Acids), where R, R', and R" represent H, NH2 or 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 Patoms. SValence Stabilizer #32: (S—)PR(—S—R)(—S—R"), where R, R', and R" Trithiophosphonic Acids represent H, NH2 or 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 Patoms. SValence Stabilizer #33: (O—)PR(-S-S-R')(—S—R") or (S—)PR(-S-S-R')(-O-R"), Phosphono(dithioperoxo)thioic Acids), where R, R', and R" represent H, NH, or Bisphosphono(dithioperoxo)thioic Acids, any organic functional group wherein the Polyphosphono(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 Patoms. SValence Stabilizer #34: (S—)PR(-S-S-R')(—S—R"), where R, R', and R" Phosphono(dithioperoxo)dithioic Acids), represent H, NH2 or any organic functional Bisphosphono(dithioperoxo)dithioic group wherein the number of carbon atoms Acids, ranges from 0 to 40, optionally having halogen Polyphosphono(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) Patoms. SValence Stabilizer #35: R-S RCSOH or R-S RCSSH for S S-(Alkylthio)thiocarboxylic Acids, S (alkylthio)thiocarboxylic and S (Arylthio)thiocarboxylic Acids, and S.S.- (arylthio)thiocarboxylic acids, and HSOCR-S-R'COSH thiobisthiocarboxylic Acids (S–S Bidentates or HSSCR S R'CSSH for S.S.- and S-S Tridentates) hiobisthiocarboxylic acids, where Rand R' represent H or any organic functional group wherein the number of carbon atoms ranges rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #36: R-S-S RCSOH 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 RCSSH Bidentates and S-S Tridentates) or S.S.-disulfidobisthiocarboxylic acids, where Rand 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 Patoms. SValence Stabilizer #37: R-CH(- SR") CH(- SR") R', and R C(- SR")=C(- SR") R', 1,2-Dithiolates, Bis(1,2-dithiolates), and where R, R', R", and R" Poly(1,2-dithiolates) (S–S Bidentates, S-S represent H, NH2 or 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 Patoms. SValence 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) for Bidentates and S-S Tetradentates) bis(rhodanines), where R and R' represent H, US 7,789,958 B2 159 160

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #39: RN=C(SH)(SH), where R represents H, NH, or 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 Patoms. SValence Stabilizer #40: RS"=C(SH)(SH) or RS C(=S)(SH), where R Thioxanthates, Bis(thioxanthates), and represents H, NH2 or 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 Patoms. SValence Stabilizer #41: RO'=C(SH)(SH) or RO C(=S)(SH), where R Xanthates, Bis(xanthates), and represents H, NH2 or 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 Patoms. SValence Stabilizer #42: Typically RR'R"P=C(SH)(SH) pentavalent Pl, Phosphinodithioformates (S–S Bidentates) although RRP C(=S) (SH) trivalent P may be acceptable in some situations, where 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. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #43: R-S-C(—S—R")—O—R' for dithioborates, R-S-C(—S—R")—S-R' Alkyl- and Aryl-Dithioborates, for trithioborates, and R-S-S-C(—S—R")—S-R' Trithioborates, Perthioborates, for perthioborates, where R, R', and Bis(dithioborates), Bis(trithioborates), and R" represent H, NH2 or 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 Patoms. SValence Stabilizer #44: R—C(—S—R")—S-R', where R, R', and R" Alkyl- and Aryl-Dithioboronates, and represent H, NH2 or 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 Patoms. SValence Stabilizer #45: (O—)As(—S—R)(—S-R')(—S—R") or (S—)As(—S—R)(—S-R')(-O-R") Trithioarsonic Acids (Arsonotrithioic or trithioarsonic acid; (O—)As(-O-R)(-S—R)(—S—R") Acids), Dithioarsonic Acids or (S—)As(—S—R)(-O-R)(-O-R") (ArSonodithioic Acids), TetrathioarSonic or dithioarSonic acid, or (S=)AS(—S—R)(—S—R)(—S—R") Acids (ArSonotetrathioic Acids), and or tetrathioarSonic acid, where R, derivatives thereof (S–S Bidentates, S-S R', and R" represent H, NH, or any organic Tridentates, S-S Tetradentates) unctional 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 Patoms. SValence Stabilizer #46: (O—)Sb(—S—R)(—S-R')(—S—R") or (S—)Sb(—S—R)(—S—R)(-O-R") Trithioantimonic Acids (Stibonotrithioic or trithioantimonic acid; Acids), Dithioantimonic Acids (O—)Sb(-O-R)(—S—R)(—S-R') or (S—)Sb(—S—R)(-O-R)(-O-R") (Stibonodithioic Acids), Tetrathioantimonic or dithioantimonic acid, or US 7,789,958 B2 161 162

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation derivatives thereof (S–S Bidentates, S-S tetrathioantimonic acid, where R, R', and R' Tridentates, S-S Tetradentates) 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. Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #47: RRR"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, NH, 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. (RS are typically aromatic or heterocyclic for phosphine P-Sulfides.) Ligand can also contain nonbinding N, O, S, or P atOnS. SValence 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, NH, 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. (RS are typically aromatic or heterocyclic for arsine As-Sulfides.) Ligand can also contain nonbinding N, O, S, or Patoms. SValence Stabilizer #49: Thiols (HS-R, HS-R-SH, etc.), where Rand 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. SValence Stabilizer #50: Sulfide (—S) ligands bound directly to the high Sulfide ligands (S Monodentates) valence metalion. PValence Stabilizer #1: PH, PHR, PHR, and PR where 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 Seatoms. PValence 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 east 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 Seatoms. PValence Stabilizer #3: R P R P R" P. R", where R, R', R", and R" Triphosphines (either P-P Bidentates or P-P-P represent H or any organic functional group Tridentates) wherein at least one wherein the number of carbon atoms ranges Phosphorus Atom is a Binding Site rom 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 Seatoms. PValence Stabilizer #4: R P R P R" P. R" P R", where R, R', R", Tetraphosphines (P-PBidentates, P-P R", and R" represent H or any organic Tridentates, or P-P Tetradentates) wherein unctional 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 Seatoms. PValence Stabilizer #5: R P R P R P R' P R' P R", where R, R', Pentaphosphines (P-PBidentates, 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. US 7,789,958 B2 163 164

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Ligand can also contain nonbinding N, P, AS, O, S, or Seatoms. PValence 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 rom 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 Seatoms. PValence 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 Seatoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. PValence 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 Seatoms. This 6-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. PValence 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 hat 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 metalion. Ring(s) can also contain O, N. S. As or Seatoms. 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. PValence 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 metalion. Ring(s) can also contain O, N. S. As or Seatoms. 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. PValence 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 Seatoms. 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. US 7,789,958 B2 165 166

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation PValence 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 Seatoms. 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. PValence 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. PValence 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. PValence 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 metalion. 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 metalion. This ligand and/or attached, uncoordinating hydrocarbon rings may or may not have halogen or polarizing or water insolubilizing groups attached. PValence 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. PValence 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 metalion. 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 metalion. This ligand and/or attached, uncoordinating hydrocarbon rings may or may not have halogen or polarizing or water insolubilizing groups attached. OValence Stabilizer #1: R-O-C(=O)—S-S-C(=O)—O—R', where R and R' Dithioperoxydicarbonic Acids, represent H, NH2 or any organic functional Bis(dithioperoxydicarbonic acids), group wherein the number of carbon atoms US 7,789,958 B2 167 168

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 Patoms. OValence Stabilizer #2: Imidodiphosphonic Acids, imidodiphosphonic acids, and (R—O—) (R Hydrazidodiphosphonic Acids, O Bis(imidodiphosphonic Acids), hydrazidodiphosphonic acids; where R, R', R", Bis(hydrazidodiphosphonic Acids), and R" represent H, NH2 or any organic Poly(imidodiphosphonic Acids), unctional 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 Patoms. OValence Stabilizer #3: Imidodiphosphonamides, or imidodiphosphonamides, and —NH-NH Hydrazidodiphosphonamides, derivatives for Bis(imidodiphosphonamides), hydrazidodiphosphonamides, where R, R', R", Bis(hydrazidodiphosphonamides), R", R", and R" represent H, NH, or 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 Patoms. OValence Stabilizer #4: (RR' N )(R" )P(=O) O P(=O)( R"R"), Diphosphonamides, where R, R', R", R", R", and R" Bis(diphosphonamides), and represent H, NH2 or 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 Patoms. OValence Stabilizer #5: R-O-C(=O)—O—R', where R, and R' represent H, Carbonates and Bis(carbonates) (O-O NH2 or 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 Patoms. OValence Stabilizer #6: RRN NR" C(=O)(OH), where Rand R' Carbazates (carbazides), Bis(carbazates), represent H, NH2 or 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 Patoms. OValence Stabilizer #7: ArSonic Acids, Bis(arsonic acids), R" represent H, NH2 or 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 Patoms. OValence Stabilizer #8: Alkyl- and Aryl- Borates and Bis(borates) represent H, NH2 or 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 Patoms. OValence Stabilizer #9: R—C(-O-R")—O-R', where R, R', and R" Alkyl- and Aryl- Boronates and represent H, NH2 or 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. US 7,789,958 B2 169 170

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Ligand can also contain nonbinding N, O, S, or Patoms. OValence Stabilizer #10: RRR"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, NH, 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. (RS are typically aromatic or heterocyclic for phosphine P-Oxides.) Ligand can also contain nonbinding N, O, S, or P atOnS. OValence 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, NH, 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. (RS are typically aromatic or heterocyclic for arsine AS-oxides.) Ligand can also contain nonbinding N, O, S, or Patoms. OValence 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 Patoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. OValence 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 metalion. Ring can also contain O, S, or Patoms. This 6-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water insolubilizing solubilizing groups attached. OValence 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 Obinding 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 metalion. Ring(s) can also contain O, S, or Patoms. 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. OValence 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 Obinding 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 metalion. Ring(s) can also contain O, S, or Patoms. 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. US 7,789,958 B2 171 172

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation OValence 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 Obinding 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 Patoms. 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. OValence 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 Obinding 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 Patoms. 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. OValence 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) OValence 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 metalion. 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. OValence 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 metalion. 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 Patoms. N-S Valence Stabilizer #2: RR N C(-NH) NR" CS NR"R" for Thioguanylureas, Guanidinothioureas, Bis(thioguanylureas), for guanidinothioureas, where R, Bis(guanidinothioureas), R", R", R", and R" represent H, NH, 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 Patoms. US 7,789,958 B2 173 174

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation N-S Valence Stabilizer #3: RR' N C(=NH)– NR" CS-R" for N Amidinothioamides, Guanidinothioamides, amidinothioamides, or RR' N C(=NH) CR"R" CS N R"R" Bis(amidinothioamides), or 2 Bis(guanidinothioamides), amidinothioacetamides, and RR' N–C(—NH)—NR" NH–CS-R" Poly(amidinothioamides), and or 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) rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. 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 rom 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 Patoms. N-S Valence Stabilizer #5: RRNCSNR"R", where R, R', R", and R" Thioureas, Bis(thioureas), and represent H, NH, 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 Patoms. 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 Patoms. 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 Patoms. N-S Valence Stabilizer #8: R-N=S—N-R', where R and R' represent Hor 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 Patoms. 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 rom 0 to 40, optionally having halogen or Tetradentates) polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. 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 unctional 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 Patoms. N-S Valence Stabilizer #11: (S-)PR( NR'R") ( OR") or (O-)PR( NR'R'')(- SR") Phosphonamidothioic Acid, or phosphonamidothioic acid, (S—)PR(—NR'R") (—SR") Phosphonamidimidodithioic Acid, orphosphonamidimidodithioic 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 US 7,789,958 B2 175 176

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or Patoms. 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 Patoms. N-S Valence Stabilizer #13: 3-Aminothioacrylamides (3-Amino-2- aminothioacrylamides, and RR' N C(=S) CR"=C( NHR") ( NR"R") thiopropenamides), 3.3- or 3.3- Diaminothioacrylamides, Bis(3- diaminothioacrylamides, where R, R, R", R", aminothioacrylamides), Bis(3,3- R", R" represent H, NH, or any organic diaminoacrylamides), Poly(3- unctional 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 Patoms. N-S Valence Stabilizer #14: 3-Aminothioacrylic Acids (3-Amino-2- or 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, NH, 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 Patoms. N-S Valence Stabilizer #15: R-C(=S)-N=CHR, where R' represents an N-Thioacyl Benzylidenimines, Bis(N- aromatic derivative (i.e. —CHs), 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) rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-S Valence Stabilizer #16: R C(=S)-C(=NOH) R', where Rand 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 Patoms. 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 Patoms. N-S Valence Stabilizer #18: o-(ON )(HS–)Ar, where Arrepresents 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 Patoms. N-S Valence Stabilizer #19: o-(NC—(CH2)o )(HS—)Ar, where Air 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 Patoms. 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 US 7,789,958 B2 177 178

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 Patoms. 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 Patoms. 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 metalion. 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, mercaptains, or uncoordinating hydrocarbons rings may or may hiocarbonyls) 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 igand 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 metalion. 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 o 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 Patoms. N-O Valence Stabilizer #2: RRNC(=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—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 Patoms. N-O Valence Stabilizer #3: RRNC(-NH)CR"R"(CO)OR", where R, R', 2-Amidinoacetates, Bis(2-amidinoacetates), R", R", and R" represent H, NH, 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 Patoms. 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 US 7,789,958 B2 179 180

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 Patoms. 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—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 Patoms. 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, NH, 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 Patoms. 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 Patoms. 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( NHR") ( NR"R") propenamides), 3,3-Diaminoacrylamides, or 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- unctional 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 Patoms. N-O Valence Stabilizer #9: 3-Aminoacrylic Acids (3-Amino-2- aminoacrylic acids, and R-O-C(=O)—CREC( O propenoic acids), 3-Hydroxy-3- or 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 he 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—O water-insolubilizing solubilizing groups Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #10: R—C(=O)-N=CHR', where R' represents an N-Acyl Benzylidenimines, Bis(N-acyl aromatic derivative (i.e. —CHs), and R represent benzylidenimines), and Poly(N-acyl H, NH2, or any organic functional group benzylidenimines) (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 Patoms. N-O Valence Stabilizer #11: o-(ON-)(RR'N—)Ar, where Arrepresents an 2-Nitroanilines (N-O Bidentates) aromatic group or heterocyclic wherein the number of carbon atoms ranges from 6 to 40, and Rand R' represent H, NH, 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 Patoms. N-O Valence Stabilizer #12: o-(NC-(CH2) )(HO )Ar, where Arrepresents 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 US 7,789,958 B2 181 182

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. N-O Valence Stabilizer #13: HetN*—O for amine N-oxides, and R-N=N*(—O)—R' Amine N-Oxides and Diazine N-Oxides or 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 Rand R' represent separate or the same aromatic unctionalities, 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 Patoms. 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) rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. 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) rom 0 to 40, optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. 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 metalion. 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 igand 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 metalion. 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 o 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) NR"R" Diamides), Thioisobiurets, Thiobiureas, 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. US 7,789,958 B2 183 184

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation formamidino thiocarbamides) Ligand can also contain nonbinding N, O, S, or Patoms. S OValence Stabilizer #2: RR'—N–C(=S)—NR"—C(=O)—R" for acyl- and Acylthioureas, Aroylthioureas, Thioacylureas, Thioaroylureas, for thioacyl- and thioaroylureas, where R, Bis(acylthioureas), Bis(aroylthioureas), R", R", and R" represent H, NH, or any Bis(thioacylureas), Bis(thioaroylu reas), 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) S OValence Stabilizer #3: Thioimidodialdehydes, Thiohydrazidodialdehydes (thioacyl for thiohydrazidodialdehydes hydrazides), Bis(thioimidodialdehydes), (thioacyl hydrazides), where R, R', and R" Bis(thiohydrazidodialdehydes), represent H, NH, 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 Patoms. S O Valence Stabilizer #4: Thioimidodicarbonic acids, for thioimidodicarbonic acids, Thiohydrazidodicarbonic acids, Bis(thioimidodicarbonic acids), R-S C(=S) NR' NH C(=O)–S-R" for Bis(thiohydrazidodicarbonic acids), thiohydrazidodicarbonic acids, where R, R', and Poly(thioimidodicarbonic acids), R" represent H, NH, 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 Patoms. S OValence Stabilizer #5: 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 Patoms. Monothioketones) (S-O Bidentates, S-O Tridentates, S. O Tetradentates) S OValence Stabilizer #6: Trithioperoxydicarbonic Diamides, trithioperoxydicarbonic diamides, and RR' N–C(=O)—S-S-C(=O)-N-R"R" Dithioperoxydicarbonic Diamides, 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 Patoms. S OValence Stabilizer #7: Dithiodicarbonic Acids, represent H, NH2 or 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 Patoms. S OValence Stabilizer #8: Trithioperoxydicarbonic Acids, represent H, NH2 or 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 Patoms. S OValence Stabilizer #9: Monothioperoxydiphosphoramide, where R, R', R", R", Bis(monothioperoxyphosphoramide), and R", R", R", and R" represent H, NH, or US 7,789,958 B2 185 186

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 Patoms. S OValence Stabilizer #10: (R-O-)(R'—O-)P(=S)—S-S-P(=O)(-O-R")(-O-R"); Monothioperoxydiphosphoric Acids, (R-O-)(R'—S—)P(=S)-S-S-P(=O)(—S—R")(-O-R"); Bis(monothioperoxyphosphoric Acids), or (R-S )(R'—S—)P(—S)-S-S-P(=O)(—S—R") (—S—R"), Poly(monothioperoxydiphosphoric Acids), where R, R', R", R", R", R", and derivatives thereof (S—O Bidentates, S-O R", and R" represent H, NH, or 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 S OValence Stabilizer #11: Monothioimidodiphosphonic Acids, Monothiohydrazidodiphosphonic Acids, Bis(monothioimidodiphosphonic Acids), Bis(monothiohydrazidodiphosphonic monothioimidodiphosphonic acids, and —NH-NH Acids), Poly(monothioimidodiphosphonic derivatives for Acid), monothiohydrazidodiphosphonic acids, where Poly(monothiohydrazidodiphosphonic R. R.R", and R" represent H, NH, or any Acids), and derivatives thereof (S-O organic functional group wherein the number of Bidentates, S. O Tridentates, S- O 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 Patoms. S OValence Stabilizer #12: (RR' N )(R" )P(=S) NH P(=O)( R") ( N R"R") Monothioimidodiphosphonamides, or monothioimidodiphosphonamides, Monothiohydrazidodiphosphonamides, and —NH-NH-derivatives for Bis(monothioimidodiphosphonamides), monothiohydrazidodiphosphonamides, where R, Bis(monothiohydrazidodiphosphonamides) R", R", R", R", and R", represent H, NH, or 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 Patoms. S OValence Stabilizer #13: (RR' N )(R" )P(=S)–S P(=O)( R")( N R"R"), Monothiodiphosphonamides, or (RR' N )(R" )P(=S)- O P(=O)(-R") ( N R"R"), Bis(monothioiphosphonamides), and where R, R', R", R", R", Poly(monothiodiphosphonamides) (S-O and R" represent H, NH2 or 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 S O Valence Stabilizer #14: Monothiodiphosphonic Acids, Bis(monothioiphosphonic Acids), Poly(monothiodiphosphonic Acids), and derivatives thereof (S—O Bidentates, S-O Tridentates, S. O Tetradentates) 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. Ligand can also contain nonbinding N, O, S, or Patoms. S OValence Stabilizer #15: (RR' N )(R" )P(=S)-S-S P(=O)( R") ( N R"R"), Monothioperoxydiphosphonamide, where R, R', R", R", R", and R" Bis(monothioperoxyphosphonamide), and represent H, NH2 or 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 Patoms. US 7,789,958 B2 187 188

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation S OValence Stabilizer #16: Monothioperoxydiphosphonic Acids, Bis(monothioperoxyphosphonic Acids), where R, R', R", and R" represent H, NH2 or 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, O Tridentates, S-O Tetradentates) optionally having halogen or polarizing or water-insolubilizing solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or Patoms. S OValence Stabilizer #17: Monothiophosphoric Acids where R, R', and R" represent H, (Phosphorothioic Acids), NH2 or 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 Patoms. S OValence Stabilizer #18: (O—)P(-S-S-R)(-O-R)(-O-R"), where R, R', Phosphoro(dithioperoxoic) Acids, and R' represent H, NH2 or any organic Bisphosphoro(dithioperoxoic) acids, functional group wherein the number of carbon Polyphosphoro (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 Patoms. S OValence Stabilizer #19: (O-)PR(-S-R')( O R") or (S-)PR(-O-R)(- O R"), Monothiophosphonic Acids where R, R', and R" represent H, NH2 or (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 Patoms. S OValence Stabilizer H2O: (O—)PR(-S-S-R')(-O-R"), where R, R', and R" Phosphono(dithioperoxoic) Acids, represent H, NH2 or any organic functional Bisphosphono(dithioperoxoic) Acids, group wherein the number of carbon atoms Polyphosphono(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 Patoms. S OValence Stabilizer #21: R-CR'(-OH)—CH2—C(=S)—R", where R, R', and Beta-Hydroxythioketones, Beta R" represent H, NH2 or 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) Patoms. S OValence Stabilizer #22: R-CR'(-SH)—CH2—C(=O)—R", where R, R', and Beta-Mercaptoketones, Beta R" represent H, NH2 or 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 mercaptoketones), 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) Patoms. S OValence Stabilizer #23: RR' N CH(-OH)– NR" C(=S) NR"R", where N-(Aminomethylol)thioureas N R, R', R", R", and R" represent H, NH, or any (Aminohydroxymethyl)thioureas), BisN 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 Patoms. 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, NH2 or any (Aminomercaptomethyl)ureas, BisN organic functional group wherein the number of (aminomethylthiol)ureas), and PolyN 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 Patoms. US 7,789,958 B2 189 190

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation S OValence Stabilizer #25: RR' N C(=S)- C(=O)- N R"R", where R, R', Monothiooxamides, R", and R" represent H, NH, any organic Bis(monothiooxamides), and unctional 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 Patoms. S OValence 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, NH2 or 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 Patoms. S OValence Stabilizer #27: R-CR'(-SH) CR"R" C(=O)(-S-R"), where R, Beta-Mercapto Thiocarboxylic Acids, R", R", R", and R" represent H, NH2 or 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 Patoms. S OValence Stabilizer #28: R-CR'(-OH) CR"R" C(=O)(-S R"), where R, Beta-Hydroxy Thiocarboxylic Acids, R", R", R", and R" represent H, NH2 or 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 Patoms. S OValence 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, NH2 or 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 Patoms. S OValence Stabilizer #30: R-S-R'COOH for S-alkylthiocarboxylic and S S-Alkylthiocarboxylic Acids, S arylthiocarboxylic acids, and HOOCR-S-R'COOH Arylthiocarboxylic Acids, and S.S.- or S.S-thiobiscarboxylic acids, where thiobiscarboxylic Acids (S-O Bidentates Rand 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 Patoms. S OValence 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 Patoms. S OValence Stabilizer #32: R—C(=O)(-S—R) for monothiomonocarboxylic Monothiomonocarboxylic Acids, Dithiodicarboxylic Acids, for Bis(monothiomonocarboxylic Acids), dithiodicarboxylic acids, where R, R', and R" Bis(dithiodicarboxylic acids), represent H, NH2 or 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 Patoms. S OValence Stabilizer #33: R-O-C(—S)-O-R', where R, and R' represent H, Monothiocarbonates and NH2 or any organic functional group wherein Bis(monothiocarbonates) (S-O Bidentates the number of carbon atoms ranges from 0 to US 7,789,958 B2 191 192

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 Patoms. S OValence Stabilizer #34: RRN NR" C(=O)(SH), where R and R' Monothiocarbazates (Monothiocarbazides), represent H, NH2 or 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 Patoms. S OValence Stabilizer #35: R-CH(—SH)—CH(-OH)—R' for alpha-mercapto Mercapto Alcohols and alcohols, R-CH(—SH)—Si(—OR)—R's for alpha Sillylmercaptoalcohols, Bis(mercapto silylmercaptoalcohols, R-CH(—SH)—R'—CH(-OH)—R" alcohols and silylmercaptoalcohols), and Poly(mercapto alcohols and or beta silylmercaptoalcohols) (S—O Bidentates, S-O silylmercaptoalcohols, etc., where R, R', R", Tridentates, S. O Tetradentates) and R" represent H, NH2 or any organic unctional 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 Patoms. S OValence Stabilizer #36: RN=C(OH)(SH), where R represents H, NH, or 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 Patoms. S OValence Stabilizer #37: R-O-C(—S—R")—O—R', where R, R', and R" Alkyl- and Aryl-Monothioborates and represent H, NH2 or 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 Patoms. S OValence Stabilizer #38: R—C(—S—R")—O—R', where R, R', and R" Alkyl- and Aryl- Monothioboronates and represent H, NH2 or 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 Patoms. S OValence Stabilizer #39: MonothioarSonic Acids (Arsonothioic where R, R', and R' Acids), Bis(monothioarsonic acids), represent H, NH2 or 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 Patoms. S OValence 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 Obinding 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 metalion. Ring(s) can also contain O, N. P. As or Seatoms. 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 US 7,789,958 B2 193 194

TABLE 5-continued Narrow Band Organic Valence Stabilizers for the Mn' and Mn' Ions General Structural Name (Type of Organic) Structural Representation 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 metalion. Ring(s) can also contain O, N. P. As or Seatoms. 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 Obinding 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 OValence 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 metalion. 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 hydrocarbonfring 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 OValence 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 metalion. 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 OValence 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 OValence Stabilizer #47: Sulfones (R-SO-R), where Rand 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