Electrocatalytic reduction of organohalides mediated by the dihalo-molybdenum phosphinic complexes trans-[MoX2(Ph2PCH2CH2PPh2)2] (X = I, Br)—A mechanistic study by cyclic voltammetry digital simulation
作者： Natércia C. T. Martins , M. Fátima C. Guedes da Silva , Riccardo Wanke , Armando J. L. Pombeiro
DOI: 10.1039/B811393A
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摘要: trans-[MoX2(dppe)2] (X = I, Br) act as inner-sphere electron-transfer mediators for the electrocatalytic reduction of organohalides RX to R˙ + X−, at both MoII→ MoI and MoI→ Mo0reduction processes, each them involving a cathodically induced heterolytic metal–halide bond cleavage with liberation X− that is followed by addition metal. Digital simulation cyclic voltammetry wide range scan rates allowed estimate rate constants various chemical steps cycles, which were compared in terms Mo–X dissociation energies, electronic stereochemical effects.
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