ORGANOMETALLIC RADICALS AS POSSIBLE ELECTROCHEMICAL OXIDATION MEDIATORS FOR [CPM(CO3)2] DIMERS (M=MO, W)

The rotating ring - disk electrode and cyclic voltammetry were used to measure the potentials and study the mechanism of the redox changes s een at platinum for the binuclear complexes of iron, molybdenum, and t ungsten: [CpFe(CO)2]2, [CpMo(CO)3]2, and [CpW(CO)3]2. The Mo and W com plexes, in contrast to the iron complexes, exhibit current yields of o xidation (reduction) of disk-generated products at the ring which subs tantially exceed the theoretical collection efficiencies. This was exp lained by assuming that organometallic radicals adsorbed on the electr ode surface can function as mediators for the oxidation of binuclear c omplexes from the solution.