Journal of Electroanalytical Chemistry, Vol.485, No.1, 42-48, 2000
Mechanistic investigation of xanthene oxidation by heterogeneous and homogeneous electron transfers
Anodic oxidation of xanthene is investigated in acetonitrile at a platinum electrode by means of cyclic voltammetric and exhaustive potentiostatic electrolysis techniques. On the voltammetric scale time, the process involves two electrons and leads to xanthydrol. The corresponding mechanism is an ECE (electron-deprotonation-electron) type; electrode reaction, the rate-determining step being the deprotonation of the cation radical obtained after the first electron transfer. On the ether hand the analysis of the oxidation by homogeneous redox catalysis is carried out, using three organic catalysts. This allows the determination of the rate constants of the homogeneous electron transfers between xanthene and catalysts, the xanthene cation radical deprotonation rare constant and the standard potential of the xanthene cation radical/xanthene couple.