CHANNEL ELECTRODE VOLTAMMETRY AND ELECTRODIMERIZATION PROCESSES - THEELECTROOXIDATION OF TRIS(DITHIOCARBAMATO)COBALT(III) COMPLEXES

Channel electro de waveshape analysis is used to demonstrate that the electro-oxidation of the tris(dithiocarbamato)cob alt(III) complexes, Co(R(2)dtc)(3), where R = Me and Et, at platinum electrodes in acetoni trile solution proceeds via an EC(2) (dimerization) mechanism in which the one-electron oxidation product, Co(R(2)dtc)(3)(+), undergoes irre versible dimerization resulting in the formation of Co-2(R(2)dtc)(5)(). Both the shift in half-wave potential and in the voltammetric shape as revealed by Tafel analysis are used to derive kinetic parameters f or the dimerization reaction, which are found to be in excellent agree ment with independently determined values.