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 acetonitrile solution proceeds via an EC(2) (dimerization) mechanism in which the one-electron oxidation product, Co(R(2)dtc)(3)(+), undergoes irreversible 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 for the dimerization reaction, which are found to be in excellent agreement with independently determined values.