Redox Disproportionation Research Articles

Deciphering the Mechanism of Base-Triggered Conversion of Ammonia to Molecular Nitrogen and Methylamine to Cyanide.

We report an in-depth investigation into the ammonia oxidation mechanism by the catalyst [RuIII(tpy)(dmabpy)NH3]3+ ([Ru(NH3)]3+). Stoichiometric reactions of [Ru(NH3)]3+ were carried out with exogenous noncoordinating bases to trigger a proposed redox disproportionation reaction, which was followed using variable-temperature NMR spectroscopy. An intermediate species was identified as a dinitrogen-bridged complex using 15N NMR and Raman spectroscopy on isotopically labeled complexes. This intermediate is proposed to derive from coupling of nitridyl species formed upon sequential redox disproportion reactions. Acetonitrile displaces the dinitrogen bridge to yield free N2. DFT calculations support this lower-energy pathway versus that previously reported for ammonia oxidation by the parent [RuIII(tpy)(bpy)NH3]3+ complex. These experimental and computational results are consistent with the interpretation of redox disproportionation involving sequential hydrogen atom transfer reactions by an amide/aminyl intermediate, [Ru(NH2)-]+ ⇔ [Ru(NH2)•]+, formed upon deprotonation of the parent complex. Control experiments employing a large excess of ammonia as a base indicate this new proposed lower-energy pathway contributes to the oxidation of ammonia to dinitrogen in conditions relevant to electrocatalysis. In addition, analogous methylamine complexes, [Ru(NH2CH3)]2+/3+, were prepared to further test the proposed mechanism. Treating [Ru(NH2CH3)]3+ with a base cleanly yields two products [Ru(NH2CH3)]2+ and [Ru(CN)]+ in an ∼3:1 ratio, fully consistent with the proposed cascade of hydrogen atom transfer reactions by an intermediate.

Do Corroles Stabilize Tetravalent Antimony?

AbstractAntimony corrole cations have been prepared by one‐electron oxidation of antimony(III) congeners with silver(I) and copper(II) salts. Isolation and crystallization was successful for the first time, and the X‐ray crystallographic investigation unraveled structural similarities with antimony(III)corroles. EPR experiments showed strong hyperfine interactions of the unpaired electron with the 121Sb (I=5/2) and 123Sb nuclei (I=7/2). A DFT analysis supports the description of the oxidized form as a SbIII corrole radical with less than 2 % SbIV character. In the presence of water or a fluoride source like PF6−, the compounds undergo a redox disproportionation to yield known antimony(III)corroles and either difluorido‐antimony(V)corroles, or bis‐μ‐oxido‐di[antimony(V)corroles] via novel cationic hydroxo‐antimony(V) derivatives.

Do Corroles Stabilize Tetravalent Antimony?

Antimony corrole cations have been prepared by one-electron oxidation of antimony(III) congeners with silver(I) and copper(II) salts. Isolation and crystallization was successful for the first time, and the X-ray crystallographic investigation unraveled structural similarities with antimony(III)corroles. EPR experiments showed strong hyperfine interactions of the unpaired electron with the 121 Sb (I=5/2) and 123 Sb nuclei (I=7/2). A DFT analysis supports the description of the oxidized form as a SbIII corrole radical with less than 2 % SbIV character. In the presence of water or a fluoride source like PF6 - , the compounds undergo a redox disproportionation to yield known antimony(III)corroles and either difluorido-antimony(V)corroles, or bis-μ-oxido-di[antimony(V)corroles] via novel cationic hydroxo-antimony(V) derivatives.

Partitioning of Fe2+ and Fe3+ between bridgmanite and silicate melt: Implications for redox evolution of the Earth's mantle

Crystallization of deep magma oceans would have created the chemical heterogeneity of the Earth's mantle. Previous geophysical studies have suggested a possible existence of the Fe3+-rich lower mantle relative to the upper mantle because the seismic profile of the Earth's lower mantle is well explained by the presence of Fe3+-rich bridgmanite. Such a contrasting distribution of Fe3+/ΣFe ratios between the upper mantle and the lower mantle could have triggered the gradual oxidation of the upper mantle by upwelling Fe3+-rich lower mantle in the early Archean around 3 billion years ago (Ga). However, whether Fe3+-rich lower mantle and Fe3+-poor upper mantle could have been formed or not in the early Earth is still poorly understood. Here we report experimental constraints on the partitioning of Fe2+ and Fe3+ between bridgmanite and silicate melt at 23–27 GPa to investigate the solid-liquid fractionation of Fe2+ and Fe3+ in the deep magma ocean. Our results show negligible fractionation of Fe2+ and Fe3+ between bridgmanite and silicate melt at the uppermost lower mantle conditions, suggesting that preferential incorporation of Fe3+ into bridgmanite during magma ocean crystallization is unlikely. If the lower mantle had become enriched in Fe3+ during the formation of the Earth, another mechanism, such as the redox disproportionation of Fe2+, may have played a more important role in controlling the Fe3+/ΣFe ratio of the mantle.

Narrow Near-Infrared Emission from InP QDs Synthesized with Indium(I) Halides and Aminophosphine.

Nonpyrophoric aminophosphines reacted with indium(III) halides in the presence of zinc chloride have emerged as promising phosphorus precursors in the synthesis of colloidal indium phosphide (InP) quantum dots (QDs). Nonetheless, due to the required P/In ratio of 4:1, it remains challenging to prepare large-sized (>5 nm), near-infrared absorbing/emitting InP QDs using this synthetic scheme. Furthermore, the addition of zinc chloride leads to structural disorder and the formation of shallow trap states inducing spectral broadening. To overcome these limitations, we introduce a synthetic approach relying on the use of indium(I) halide, which acts as both the indium source and reducing agent for aminophosphine. The developed zinc-free, single-injection method gives access to tetrahedral InP QDs with an edge length > 10 nm and narrow size distribution. The first excitonic peak is tunable from 450 to 700 nm by changing the indium halide (InI, InBr, InCl). Kinetic studies using phosphorus NMR reveal the coexistence of two reaction pathways, the reduction of transaminated aminophosphine by In(I) and via redox disproportionation. Etching the surface of the obtained InP QDs at room temperature with in situ-generated hydrofluoric acid (HF) leads to strong photoluminescence (PL) emission with a quantum yield approaching 80%. Alternatively, surface passivation of the InP core QDs was achieved by low-temperature (140 °C) ZnS shelling using the monomolecular precursor zinc diethyldithiocarbamate. The obtained InP/ZnS core/shell QDs that emit in a range of 507-728 nm exhibit a small Stokes shift (110-120 meV) and a narrow PL line width (112 meV at 728 nm).

Metal-Ligand Cooperativity in Iron Dinitrogen Complexes: Proton-Coupled Electron Transfer Disproportionation and an Anionic Fe(0)N2 Hydride.

Metal-ligand cooperativity and redox-active ligands enable the use of open-shell first-row transition metals in catalysis. However, the fleeting nature of the reactive intermediates prevents direct inspection of the relevant catalytic species. By employing phosphine α-iminopyridine (PNN)-based complexes, we show that chemical and redox metal-ligand cooperativity can be combined in the coordination sphere of iron dinitrogen complexes. These systems show dual activation modes either through deprotonation, which triggers reversible core dearomatization, or through reversibly accepting one electron by reducing the imine functionality. (PNN)Fe(N2) fragments can be obtained under mildly reducing conditions. Deprotonation of such complexes induces dearomatization of the pyridine core while retaining a terminally coordinated N2 ligand. This species is nevertheless stable in solution only below -30 °C and undergoes unusual ligand-assisted redox disproportionation through proton-coupled electron transfer at room temperature. The origin of this phenomenon is the significant lability of the α-imine C-H bonds in the dearomatized species, where the calculated bond dissociation free energy is 48.7 kcal mol-1. The dispropotionation reaction yields an overreduced iron compound, demonstrating that the formation of such species can be triggered by mild bases, and does not require harsh reducing agents. Reaction of the dearomatized species with dihydrogen yields a rare anionic Fe hydride that binds dinitrogen and features a rearomatized core.

Zero-emission multivalorization of light alcohols with self-separable pure H2 fuel

To reach Paris Agreement’s target of 1.5 °C global temperature increase by 2100, low emission strategies are crucial. In synthetic chemistry, the phototransformation of light alcohols (methanol, ethanol and iso-propanol) into hydrogen fuel and chemicals promises high potential utility value for industry. However, this process is often practiced using promoters (i.e. water, acid or base), with and several issues remained unsolved, e.g. water promoter induce CO2 emission; acid/base promoters restrict catalyst selection, and lead to complicated product purification and cost increase. In this work, we report solar-driven promoter-free multivalorization of light alcohols into self-separable hydrogen gas/fuel and liquid chemicals without COx emission based on the two-dimensional (2D) SnS/g-C3N4 heterojunction. The hydrogen production efficiency reaches 1.27 mmol.g−1. h−1 with ∼ 95 % recoverability. The process reduction occurs via a sequence of redox reactions, combination and disproportionation, as confirmed from experimental and product analysis. This work demonstrates the effectiveness of 2D heterojunctions for promoter-free, zero-emission alcohol phototransformations.

Quasilinear 3d-metal(i) complexes [KM(N(Dipp)SiR3)2] (M = Cr-Co) - structural diversity, solution state behaviour and reactivity.

The synthesis and characterization of neutral quasilinear 3d-metal(i) complexes of chromium to cobalt of the type [KM(N(Dipp)SiMe3)2] (Dipp = 2,6-di-iso-propylphenyl) are reported. In solid state these metal(i) complexes either occur as isolated molecules (Co) or are part of a potassium ion linked 1D-coordination polymer (Cr-Fe). In solution the potassium cation is either ligated within the ligand sphere of the metal silylamide or is separated from the complex depending on the solvent. For iron, we showcase that it is possible to use sodium or lithium metal for the reduction of the metal(ii) precursor. However, in these cases the resulting iron(i) complexes can only be isolated upon cation separation using an appropriate crown-ether. Further, the neutral metal(i) complexes are used to introduce NBu4+ as an organic cation in the case of cobalt and iron. The impact of the intramolecular cation complexation was further demonstrated upon reaction with diphenyl acetylene which leads to bond formation processes and redox disproportionation instead of η2-alkyne complex formation.

Highly Oxidized Ellagitannins of Carpinus japonica and Their Oxidation-Reduction Disproportionation.

In the research on ellagitannin metabolism, two unique dehydroellagitannins, carpinins E (1) and F (2), bearing dehydrohexahydroxydiphenoyl (DHHDP) and hydrated biscyclohexenetrione dicarboxyl ester (HBCHT) groups, were isolated from young leaves of Carpinus japonica. Upon heating in H2O or treatment with pH 6 buffer at room temperature, 1 and 2 afforded the reduction product 3, isocarpinin A, with an (R)-hexahydroxydiphenoyl (HHDP) group, suggesting the occurrence of redox disproportionation of the (S)-DHHDP group. This was supported by the increase in production of 3 in the pH 6 buffer solution by coexistence of epigallocatechin-3-O-gallate (15), accompanied by oxidation of 15. In contrast, treatment of 1 and 2 with ascorbic acid yielded 4, carpinin A, with an (S)-HHDP group. Upon heating with ascorbic acid, the HBCHT group was also reduced to an (S)-HHDP group, and 2 was converted to 2,3;4,6-bis(S)-HHDP glucose. In leaves of C. japonica, the tannins 1 and 2 are dominant in young spring leaves, but compounds 3 and 4 become the major components of tannins in mature leaves. These results suggest that, in ellagitannin biosynthesis, oxidative coupling of the two galloyl groups first generates a DHHDP group, and subsequent reduction of DHHDP esters produces HHDP esters.

Three-Coordinate Copper(II) Alkynyl Complex in C-C Bond Formation: The Sesquicentennial of the Glaser Coupling.

Copper(II) alkynyl species are proposed as key intermediates in numerous Cu-catalyzed C-C coupling reactions. Supported by a β-diketiminate ligand, the three-coordinate copper(II) alkynyl [CuII]-C≡CAr (Ar = 2,6-Cl2C6H3) forms upon reaction of the alkyne H-C≡CAr with the copper(II) tert-butoxide complex [CuII]-OtBu. In solution, this [CuII]-C≡CAr species cleanly transforms to the Glaser coupling product ArC≡C-C≡CAr and [CuI](solvent). Addition of nucleophiles R'C≡C-Li (R' = aryl, silyl) and Ph-Li to [CuII]-C≡CAr affords the corresponding Csp-Csp and Csp-Csp2 coupled products RC≡C-C≡CAr and Ph-C≡CAr with concomitant generation of [CuI](solvent) and {[CuI]-C≡CAr}-, respectively. Supported by density functional theory (DFT) calculations, redox disproportionation forms [CuIII](C≡CAr)(R) species that reductively eliminate R-C≡CAr products. [CuII]-C≡CAr also captures the trityl radical Ph3C· to give Ph3C-C≡CAr. Radical capture represents the key Csp-Csp3 bond-forming step in the copper-catalyzed C-H functionalization of benzylic substrates R-H with alkynes H-C≡CR' (R' = (hetero)aryl, silyl) that provide Csp-Csp3 coupled products R-C≡CR via radical relay with tBuOOtBu as oxidant.

A hemilabile diphosphine pyridine pincer ligand: σ- and π-binding in molybdenum coordination complexes

A series of molybdenum compounds supported by a hemilabile pyridine diphosphine pincer ligand have been synthesized. The ligand demonstrates variable binding modes, adapting to the electronic and geometric requirements of the metal center. In Mo0 and MoII polycarbonyl complexes, coordination through the σ-donating pyridine nitrogen lone pair is observed. Upon oxidative group transfer with anionic azide, a MoIV nitride compound is formed, accompanied by a change in the ancillary ligand binding mode to the pyridine π-system. The σ-coordination was restored by subsequent functionalization of the nitride moiety with either silyl electrophiles or protons. Protonation results in redox disproportionation with concomitant nitride functionalization. Characterization by single crystal X-ray diffraction, nuclear magnetic resonance, and infrared spectroscopy is discussed.

(Invited) Electrocatalytic Ammonia Oxidation

Much of the global effort toward producing solar fuels has involved splitting water to obtain molecular hydrogen. Unfortunately, hydrogen gas has a relatively low energy-per-volume, and extreme cryogenic temperature and pressure is needed to bring hydrogen to a condensed state. An interesting choice for a hydrogen storage medium that circumvents these setbacks is ammonia. Synthesis of ammonia (largely via the Haber-Bosch process) is already the second-largest chemical industrial process in the world, and as a result the infrastructure for ammonia storage and transport already exists. Ammonia can be easily liquefied under 10 bar of pressure which leads to a three-fold higher energy density than hydrogen gas in state-of-the-art carbon fiber cylinders. One significant bottleneck limiting the use of ammonia for hydrogen storage is the inability to efficiently extract hydrogen from ammonia on-demand.Electrolysis offers a convenient route to decompose ammonia into nitrogen and hydrogen, which potentially only requires 0.1 V. However, there is a lack of fundamental understanding of the reactions involved in the electrolysis. In this talk, the electrolysis of liquid ammonia with heterogeneous catalysts, as well as ammonia dissolved in non-aqueous solvents, using two and three electrode measurements, will be presented.1,2 The possible mechanisms of the anodic and cathodic reactions will be discussed, as well as the cause and magnitude of the related overpotentials which limit the efficiency. Further, while there have been multiple reports on heterogeneous catalysts for electrocatalytic oxidation of NH3, with limited success, homogenous molecular catalysts have been non-existent until now.3 A transition metal complex, [Ru(tpy)(dmabpy)NH3]2+ (tpy = 2,2′:6′,2′′-terpyridine, dmabpy = 4,4'-dimethylamino-2,2'-bipyridine), will be presented which shows the first example of electrocatalytic activity in presence of ammonia at room temperature and ambient pressure. Gas chromatography measurements reveals production of N2 and H2 in a 1:3 ratio following bulk electrolysis of ammonia. Absorption measurements following reaction of [Ru(tpy)(dmabpy)NH3]3+ with one equivalent of ammonia clearly show regeneration of [Ru(tpy)(dmabpy)NH3]2+ which provides evidence of redox disproportionation to produce a Ru(IV) imido species as an intermediate in formation of the N-N bond. Nitrogen isotope labeling experiments reveal incorporation of the coordinated amine with free ammonia in solution to produce dinitrogen. Results from cyclic voltammetry, stopped-flow, NMR and rotating ring-disc measurements will also be presented. From these combined results, a tentative mechanism will be presented and the implications discussed.1) Little, D.J., Smith, M.R., Hamann, T.W.; “Electrolysis of Liquid Ammonia for Hydrogen Generation” Energy & Environmental Science, 2015, 8, 2775 – 27812) Little, D.J., Edwards, D., Smith, M.R., Hamann, T.W.; “As Precious as Platinum: Iron Nitride for Electrocatalytic Oxidation of Liquid Ammonia” ACS Applied Materials & Interfaces 2017, 9 (19), 16228 – 162353) Habib-Zadeh, F., Miller, S.L., Hamann, T.W., Smith, M.R.; “Homogenous Electro-Catalytic Oxidation of Ammonia to N2 Under Mild Conditions” Proceedings of the National Academy of Science 2019, 116 (8) 2849 – 2853

Cu2O nanocubes with mixed oxidation-state facets for (photo)catalytic hydrogenation of carbon dioxide

Cuprous oxide (Cu2O), an earth-abundant, low-cost metal-oxide semiconductor, has received enormous attention for its CO2 reduction ability in aqueous media by photochemical, photoelectrochemical and electrochemical methods. An unresolved problem with all of these approaches, however, is the instability of the Cu2O caused by its tendency to undergo an irreversible redox disproportionation reaction. Here, we report a way to circumvent this troublesome behaviour of Cu2O by driving the CO2 reduction in the gas-phase via heterogeneous photocatalytic hydrogenation. To this end, Cu2O nanocubes with surfaces comprising mixed oxidation-state copper Cu(0,I,II) sites, oxygen vacancies [O] and hydroxyl OH groups were synthesized. These surfaces enable heterolysis of H2 and adsorption of CO2 under mild conditions; they facilitate the reverse water–gas shift reaction, while rendering the redox disproportionation reaction reversible. This synergism provides Cu2O nanocubes with high photocatalytic activity and stability. Cu2O is a promising photocatalyst, although its stability is compromised by a disproportionation reaction that leads to the formation of Cu and CuO. Now, a method is reported to stabilize Cu2O nanocubes, rendering them highly active and stable for the photocatalytic reverse water–gas shift reaction.

Mechanisms of Cobalt/Phosphine‐Catalyzed Cross‐Coupling Reactions

>The combination of CoCl2 with bidentate phosphines is known to catalyze challenging cross-coupling and Heck-type reactions, but the mechanisms of these valuable transformations have not been established. Here, we use electrospray-ionization mass spectrometry to intercept the species formed in these reactions. Our results indicate that a sequence of transmetalation, reductive elimination, and redox disproportionation convert the cobalt(II) precatalyst into low-valent cobalt complexes. These species readily transfer single electrons to alkyl bromides, which thereupon dissociate into alkyl radicals and Br- . In cross-coupling reactions, the alkyl radicals add to the cobalt catalyst to form observable heteroleptic complexes, which release the coupling products through reductive eliminations. In the Heck-type reactions, the low abundance of newly formed ionic species renders the analysis more difficult. Nonetheless, our results also point to the occurrence of single-electron transfer processes and the involvement of radicals in these transformations.

Mechanistic Features of the Oxidation-Reductive Coupling of Alcohols Catalyzed by Oxo-Vanadium Complexes.

The oxo-vanadium-catalyzed redox disproportionation of activated alcohols (oxidation-reductive coupling, Ox-RC) produces carbonyl compounds and hydrocarbon dimers. A mechanistic study of this novel reaction is reported herein. Following our initial disclosure, new findings include the following: (1) The [(salimin)VO2]--catalyzed Ox-RC of Ph2CHOH in the presence of fluorene affords the products of H-atom abstraction and all possible hydrocarbon dimers. (2) Electronic substituent effects on the relative rates of Ox-RC with respect to 4-X-BnOH reactants and Bu4N[(Y-salimin)VO2] catalysts (1a-c) reveal (a) a correlation of the oxidation rate of X-BnOH reactants with the radical σ parameter and (b) correlation of the oxidation rate for (Y-salimin)VO2- with the standard Hammett σ parameter. (3) The ease of electrochemical reduction of 1a-c is Y = NO2 > OMe > H. (4) Ambient 1H NMR studies of the interaction of 1 with alcohols suggest only a weak equilibrium association. (5) Density functional theory computational modeling of the Ox-RC reaction supports a ping-pong-type catalytic pathway, beginning with alcohol oxidation by (salimin)VO2-, preferably by stepwise-H-atom transfer from the alcohol to 1, affording the carbonyl product and the reduced (salimin)V(III)(OH)2-. The reduction half-reaction likely begins with condensation of the latter species with R2CHOH to give the alkoxide complex (salimin)V(OR)OH-; homolysis of the R···OV(III)(salimin) bond affords (salimin)V(IV)OH(O)- and the R-radical; the latter dimerizes and the former can disproportionate via H-transfer to reform catalyst (salimin)VO2- (1) and (salimin)V(OH)2-.

Expanding the Scope of Ligand Substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) To Afford New Heteroleptic Dithiolene Complexes.

The scope of direct substitution of the dithiolene ligand from [M(S2C2Ph2)2] [M = Ni2+ (1), Pd2+ (2), Pt2+ (3)] to produce heteroleptic species [M(S2C2Ph2)2Ln] (n = 1, 2) has been broadened to include isonitriles and dithiooxamides in addition to phosphines and diimines. Collective observations regarding ligands that cleanly produce [M(S2C2Ph2)Ln], do not react at all, or lead to ill-defined decomposition identify soft σ donors as the ligand type capable of dithiolene substitution. Substitution of MeNC from [Ni(S2C2Ph2)(CNMe)2] by L provides access to a variety of heteroleptic dithiolene complexes not accessible from 1. Substitution of a dithiolene ligand from 1 involves net redox disproportionation of the ligands from radical monoanions, -S•SC2Ph2, to enedithiolate and dithione, the latter of which is an enhanced leaving group that is subject to further irreversible reactions.

Three-Coordinate Copper(II) Aryls: Key Intermediates in C-O Bond Formation.

Copper(II) aryl species are proposed key intermediates in Cu-catalyzed cross-coupling reactions. Novel three-coordinate copper(II) aryls [CuII]-C6F5 supported by ancillary β-diketiminate ligands form in reactions between copper(II) alkoxides [CuII]-OtBu and B(C6F5)3. Crystallographic, spectroscopic, and DFT studies reveal geometric and electronic structures of these Cu(II) organometallic complexes. Reaction of [CuII]-C6F5 with the free radical NO(g) results in C-N bond formation to give [Cu](η2-ONC6F5). Remarkably, addition of the phenolate anion PhO- to [CuII]-C6F5 directly affords diaryl ether PhO-C6F5 with concomitant generation of the copper(I) species [CuI](solvent) and {[CuI]-C6F5}-. Experimental and computational analysis supports redox disproportionation between [CuII]-C6F5 and {[CuII](C6F5)(OPh)}- to give {[CuI]-C6F5}- and [CuIII](C6F5)(OPh) unstable toward reductive elimination to [CuI](solvent) and PhO-C6F5.

N-heterocyclic carbene formation induced fluorescent and colorimetric sensing of fluoride using perimidinium derivatives.

In this study, two perimidinium derivatives (1 and 2) were designed, synthesized, and developed as efficient fluorescent and colorimetric chemodosisensors for F(-) in DMSO or more competitive media (DMSO containing 10 % water). In the presence of F(-) , the yellow and non-fluorescent solution of 1/2 became colourless and exhibited strong blue fluorescence. This unique spectroscopic behaviour of 1/2 towards F(-) was attributed to the formation of N-heterocyclic carbene deprotonated by F(-) , which immediately reacted with water to give a colourless and fluorescent carbinol. Interestingly, it was found that this carbinol intermediate was unstable and further underwent a redox disproportionation to generate two other optically changed compounds. All the proposed mechanisms for the sensing process have been carefully confirmed by experiments.

Classical and non-classical redox reactions of Pd(II) complexes containing redox-active ligands.

Reactivity studies of a Pd(II)-verdazyl complex reveal novel ligand-centred reduction processes which trigger pseudo-reductive elimination at Pd. Reaction of the complex with water induces a ligand-centred redox disproportionation. The reduced verdazyl ligands can also be reversibly protonated.

Disulfiram, Metals, and Melanoma

A two-session general chemistry laboratory experiment is described concerning redox transformations of disulfiram, the disulfide of diethyldithiocarbamate (deDTC), related to its use in clinical trials for treatment of melanoma. In this laboratory, the students follow three different procedures to synthesize the complex Cu(deDTC)2 using sodium diethyldithiocarbamate, Na(deDTC)·3H2O; disulfiram, DSF; and an oxidized analogue, bis(dialkyliminium) tetrathiolane dication, (bitt-4)2+, as starting materials. The first method is essentially quantitative and has been used as an analytic method for trace metal detection as characterized by colorimetric analysis. The Zn, Ni, and Fe complexes are also synthesized and spectrally characterized. The latter two pathways involve redox disproportionation reactions of the sulfur compounds in which the stoichiometric ratios are obtained by balancing equations. Precipitation analysis is also used to qualitatively identify byproducts of the disproportionation reactions.