title: Electrocatalytic reduction of organohalides mediated by the dihalo-molybdenum phosphinic complexes trans-[MoX(2)(Ph(2)PCH(2)CH(2)PPh(2))(2)] (X = I, Br)-A mechanistic study by cyclic voltammetry digital simulation.
abstract: trans-[MoX(2)(dppe)(2)] (X = I, Br) act as inner-sphere electron-transfer mediators for the electrocatalytic reduction of organohalides RX to R + X(-), at both Mo(II)--> Mo(I) and Mo(I)--> Mo(0) reduction processes, each of them involving a cathodically induced heterolytic metal-halide bond cleavage with liberation of X(-) that is followed by addition of RX to the metal. Digital simulation of cyclic voltammetry at a wide range of scan rates allowed to estimate the rate constants of the various chemical steps for both electrocatalytic cycles, which were compared in terms of Mo-X bond dissociation energies, electronic and stereochemical effects.
authors.affiliation: Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisboa, Portugal.
authors.forename: Natércia C T
authors.initials: NC
authors.lastname: Martins
authors.forename: M Fátima C
authors.initials: MF
authors.lastname: Guedes da Silva
authors.forename: Riccardo
authors.initials: R
authors.lastname: Wanke
authors.forename: Armando J L
authors.initials: AJ
authors.lastname: Pombeiro