Channel electrode voltammetry and electrodimerization processes. The electro-oxidation of tris(dithiocarbamato)cobalt(III) complexes

Channel electrode waveshape analysis is used to demonstrate that the electro-oxidation of the tris(dithiocarbamato)cobalt(III) complexes, Co(R₂dtc)₃, where R = Me and Et, at platinum electrodes in acetonitrile solution proceeds via an EC₂ (dimerization) mechanism in which the one-electron oxidation product, Co(R₂dtc)⁺₃, undergoes irreversible dimerization resulting in the formation of Co₂(R₂dtc)⁺₅. Both the shift in half-wave potential and in the voltammetric shape as revealed by Tafel analysis are used to derive kinetic parameters for the dimerization reaction, which are found to be in excellent agreement with independently determined values.