Kinetics of the Chemical and Electrochemical, Reversible Oxidation of Bis(dithiooxalato-S,S')cuprate(II), 2-. A Facile, Light-Activated, Intramolecular Electron Transfer and Cleavage of the C-C Bond in the Coordinated Dto Ligands in the - Anion

Article abstract of DOI:10.1021/ja00316a028

The rates of reaction of bis(dithiooxalato-S,S')cuprate(II), ^2-, with Cu(II) and Fe(III) have been measured and the corresponding rate constants and activation parameters are reported.In addition, the electrochemistry of this complex and of the oxidation product ^- was studied in detail.The ^- anion undergoes a light-activated, intramolecular, Dto -> Cu two-electron transfer with cleavage of the C-C bond in the Dto ligand and generation of gaseous SCO.Addition of triphenylphosphine to ^- in the presence or absence of light also results in intramolecular redox and cleavage of the C-C bond.