The catalytic oxidation of pyrrole by the [(salen)VIVOVV(salen)]3+ cation, which is formed on an electrode surface by the oxidation of [(salen)VIVOVIV(salen)]2+, was examined by hydrodynamic voltammetry at a rotating glassy carbon disk electrode. The electron transfer rate constant for the cross-reaction [(salen)VOV(salen)]3+/pyrrole was estimated to be 4 × 104 mol-1 cm3 s-1. O2-oxidation of the [(salen)VOV(salen)]+ cation gives rise to the catalysis for the O2-oxidative polymerization of pyrrole. The polymerization was rate-determined by the reoxidation step of the catalyst by O2.
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