Electrochemical and chemical properties of dithiocarbamato complexes of ruthenium(II), ruthenium(III), and ruthenium(IV)

S. H. Wheeler, Bruce 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 (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.

Original languageEnglish
Pages (from-to)340-350
Number of pages11
JournalInorganic Chemistry
Volume17
Issue number2
StatePublished - 1978
Externally publishedYes

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Ruthenium
Electrochemical properties
chemical properties
Chemical properties
ruthenium
Electrochemical oxidation
Carbon Monoxide
Oxidation
Electrons
products
electrochemical oxidation
Redox reactions
Methylene Chloride
Isomerization
propylene
Electrolysis
oxidation
carbonates
Gases
Metals

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Electrochemical and chemical properties of dithiocarbamato complexes of ruthenium(II), ruthenium(III), and ruthenium(IV). / Wheeler, S. H.; Mattson, Bruce M.; Miessler, G. L.; Pignolet, L. H.

In: Inorganic Chemistry, Vol. 17, No. 2, 1978, p. 340-350.

Research output: Contribution to journalArticle

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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 (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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AU - Mattson, Bruce 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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