Electrochemical and Chemical Properties of Dithiocarbamato Complexes of Ruthenium(II), Ruthenium(III), and Ruthenium(IV)

S. H. Wheeler; B. M. Mattson; G. L. Miessler; L. H. Pignolet

doi:10.1021/ic50180a034

Electrochemical and Chemical Properties of Dithiocarbamato Complexes of Ruthenium(II), Ruthenium(III), and Ruthenium(IV)

S. H. Wheeler, B. M. Mattson, G. L. Miessler, L. H. Pignolet

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Abstract

An electrochemical study of several N,N-diethyldithiocarbamato (Et₂dtc) complexes of Ru(II), Ru(III), and Ru(IV) was carried out. [(CO)Ru(dtc)₂]₂. Ru(dtc)₃, and ClRu(dtc)₃ were studied by dc, ac, and cyclic voltammetric techniques in the solvents acetonitrile, propylene carbonate, and methylene chloride. The results indicate that the bimetallic complexes α- and β-[Ru₂(dtc)₅]⁺ are not formed as primary electrochemical oxidation products of Ru(dtc)₃ or reduction products of ClRu(dtc)₃. The electrochemical oxidation product of Ru(dtc)₃ in CH₃CN is [(CH₃CN)Ru(dtc)₃]⁺, and the metal-containing reduction product of ClRu(dtc)₃, which exists as [(CH₃CN)Ru(dtc)₃]⁺Cl^- in CH₃CN, is Ru(dtc)₃. In propylene carbonate, ClRu(dtc)₃ is undissociated and exhibits a one-electron oxidation (E_1/2 = 0.97 V) and a two-electron reduction (E_1/2 = -0.77 V) to Ru(dtc)₃ ^-. [(CO)Ru(dtc)₂]₂ shows an irreversible one-electron oxidation with E_1/2 = 0.86 V vs. SCE in CH₂Cl₂. The electrolysis products of these complexes are compared to chemical redox products and redox mechanisms are discussed. Various redox reactions of the mixed-valence complexes Ru₂(dtc)₅, Ru(dtc)₅ ⁺, ClRu(dtc)₃, and Ru(dtc)₃ have been examined. Oxidation and isomerization reactions of Ru(dtc)₃ and α-[Ru₂(dtc)₅]⁺ using BF₃ gas have been studied in detail, and reaction mechanisms are proposed. The ¹NMR spectra of α- and β-[Ru₂(Me₂dtc)₅]⁺ have been assigned by variable-temperature and ligand-exchange studies.

Original language	English (US)
Pages (from-to)	340-350
Number of pages	11
Journal	Inorganic Chemistry
Volume	17
Issue number	2
DOIs	https://doi.org/10.1021/ic50180a034
State	Published - Jan 1 1978
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic50180a034

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Wheeler, S. H., Mattson, B. M., Miessler, G. L., & Pignolet, L. H. (1978). Electrochemical and Chemical Properties of Dithiocarbamato Complexes of Ruthenium(II), Ruthenium(III), and Ruthenium(IV). Inorganic Chemistry, 17(2), 340-350. https://doi.org/10.1021/ic50180a034

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title = "Electrochemical and Chemical Properties of Dithiocarbamato Complexes of Ruthenium(II), Ruthenium(III), and Ruthenium(IV)",

abstract = "An electrochemical study of several N,N-diethyldithiocarbamato (Et2dtc) complexes of Ru(II), Ru(III), and Ru(IV) was carried out. [(CO)Ru(dtc)2]2. Ru(dtc)3, and ClRu(dtc)3 were studied by dc, ac, and cyclic voltammetric techniques in the solvents acetonitrile, propylene carbonate, and methylene chloride. The results indicate that the bimetallic complexes α- and β-[Ru2(dtc)5]+ are not formed as primary electrochemical oxidation products of Ru(dtc)3 or reduction products of ClRu(dtc)3. The electrochemical oxidation product of Ru(dtc)3 in CH3CN is [(CH3CN)Ru(dtc)3]+, and the metal-containing reduction product of ClRu(dtc)3, which exists as [(CH3CN)Ru(dtc)3]+Cl- in CH3CN, is Ru(dtc)3. In propylene carbonate, ClRu(dtc)3 is undissociated and exhibits a one-electron oxidation (E1/2 = 0.97 V) and a two-electron reduction (E1/2 = -0.77 V) to Ru(dtc)3 -. [(CO)Ru(dtc)2]2 shows an irreversible one-electron oxidation with E1/2 = 0.86 V vs. SCE in CH2Cl2. The electrolysis products of these complexes are compared to chemical redox products and redox mechanisms are discussed. Various redox reactions of the mixed-valence complexes Ru2(dtc)5, Ru(dtc)5 +, ClRu(dtc)3, and Ru(dtc)3 have been examined. Oxidation and isomerization reactions of Ru(dtc)3 and α-[Ru2(dtc)5]+ using BF3 gas have been studied in detail, and reaction mechanisms are proposed. The 1NMR spectra of α- and β-[Ru2(Me2dtc)5]+ have been assigned by variable-temperature and ligand-exchange studies.",

author = "Wheeler, {S. H.} and Mattson, {B. M.} and Miessler, {G. L.} and Pignolet, {L. H.}",

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T1 - Electrochemical and Chemical Properties of Dithiocarbamato Complexes of Ruthenium(II), Ruthenium(III), and Ruthenium(IV)

AU - Wheeler, S. H.

AU - Mattson, B. M.

AU - Miessler, G. L.

AU - Pignolet, L. H.

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N2 - An electrochemical study of several N,N-diethyldithiocarbamato (Et2dtc) complexes of Ru(II), Ru(III), and Ru(IV) was carried out. [(CO)Ru(dtc)2]2. Ru(dtc)3, and ClRu(dtc)3 were studied by dc, ac, and cyclic voltammetric techniques in the solvents acetonitrile, propylene carbonate, and methylene chloride. The results indicate that the bimetallic complexes α- and β-[Ru2(dtc)5]+ are not formed as primary electrochemical oxidation products of Ru(dtc)3 or reduction products of ClRu(dtc)3. The electrochemical oxidation product of Ru(dtc)3 in CH3CN is [(CH3CN)Ru(dtc)3]+, and the metal-containing reduction product of ClRu(dtc)3, which exists as [(CH3CN)Ru(dtc)3]+Cl- in CH3CN, is Ru(dtc)3. In propylene carbonate, ClRu(dtc)3 is undissociated and exhibits a one-electron oxidation (E1/2 = 0.97 V) and a two-electron reduction (E1/2 = -0.77 V) to Ru(dtc)3 -. [(CO)Ru(dtc)2]2 shows an irreversible one-electron oxidation with E1/2 = 0.86 V vs. SCE in CH2Cl2. The electrolysis products of these complexes are compared to chemical redox products and redox mechanisms are discussed. Various redox reactions of the mixed-valence complexes Ru2(dtc)5, Ru(dtc)5 +, ClRu(dtc)3, and Ru(dtc)3 have been examined. Oxidation and isomerization reactions of Ru(dtc)3 and α-[Ru2(dtc)5]+ using BF3 gas have been studied in detail, and reaction mechanisms are proposed. The 1NMR spectra of α- and β-[Ru2(Me2dtc)5]+ have been assigned by variable-temperature and ligand-exchange studies.

AB - An electrochemical study of several N,N-diethyldithiocarbamato (Et2dtc) complexes of Ru(II), Ru(III), and Ru(IV) was carried out. [(CO)Ru(dtc)2]2. Ru(dtc)3, and ClRu(dtc)3 were studied by dc, ac, and cyclic voltammetric techniques in the solvents acetonitrile, propylene carbonate, and methylene chloride. The results indicate that the bimetallic complexes α- and β-[Ru2(dtc)5]+ are not formed as primary electrochemical oxidation products of Ru(dtc)3 or reduction products of ClRu(dtc)3. The electrochemical oxidation product of Ru(dtc)3 in CH3CN is [(CH3CN)Ru(dtc)3]+, and the metal-containing reduction product of ClRu(dtc)3, which exists as [(CH3CN)Ru(dtc)3]+Cl- in CH3CN, is Ru(dtc)3. In propylene carbonate, ClRu(dtc)3 is undissociated and exhibits a one-electron oxidation (E1/2 = 0.97 V) and a two-electron reduction (E1/2 = -0.77 V) to Ru(dtc)3 -. [(CO)Ru(dtc)2]2 shows an irreversible one-electron oxidation with E1/2 = 0.86 V vs. SCE in CH2Cl2. The electrolysis products of these complexes are compared to chemical redox products and redox mechanisms are discussed. Various redox reactions of the mixed-valence complexes Ru2(dtc)5, Ru(dtc)5 +, ClRu(dtc)3, and Ru(dtc)3 have been examined. Oxidation and isomerization reactions of Ru(dtc)3 and α-[Ru2(dtc)5]+ using BF3 gas have been studied in detail, and reaction mechanisms are proposed. The 1NMR spectra of α- and β-[Ru2(Me2dtc)5]+ have been assigned by variable-temperature and ligand-exchange studies.

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