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

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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