Elucidation of the Wide Range of Reaction Pathways That Accompany the Electrochemical Oxidation of cis,mer-[Mn(CO)(2)(eta(1)-dpm)(eta(2)-dpm)X] (dpm = Ph(2)PCH(2)PPh(2); X = Cl, Br).

The electrochemical oxidation of cis,mer-[Mn(CO)(2)(eta(1)-dpm)(eta(2)-dpm)Br] (dpm = Ph(2)PCH(2)PPh(2)), or (cis,mer)(0),()()has been examined in dichloromethane (0.1 M Bu(4)NPF(6)) by voltammetric, bulk electrolytic, in situ and ex situ spectroelectrochemical and simulation techniques. On the voltammetric time scale at 20 degrees C, the neutral 18-electron cis,mer Mn(I) species is oxidized to the corresponding 17-electron cation which at slow scan rates isomerizes to the trans cation.