Chemistry, Vol 11, No 4 (2018)

Effect of Ligands at the Platinum in Binuclear Manganese-Platinum Phenylvinylidene Complexes on their Redox Properties

Galina Veniaminovna Burmakina, Victor Vasilievich Verpikin, Dmitry Valerievich Zimonin, Oleg Sergeevich Chudin, Anatoly Iosiphovich Rubaylo

Abstract


The redox properties of binuclear μ-vinylidene complexes Cp(CO)2MnPt(µ-C1=C2HPh)(L)(L') [L = L' = PPh3 (1); L = PPh2H; L' = PPh3 (2); L = CO, L' = PPh3 (3); L = L' = P(OPri)3 (4); L = PPh2H; L' = P(OPri)3 (5); L = CO, L' = P(OPri)3 (6)] were studied by electrochemical methods at a platinum, a glassed carbon and a dropping mercury electrodes in acetonitrile solutions. The redox values of complexes 1-6 were shown to depend on the nature of phosphorus containing ligands at the palladium center. It was established that one-electron oxidation of 1, 2, 4, 5 results in a cleavage of the Mn-Pt and Pt-C1 bonds affording vinylidene complex Cp(CO)2Mn=C=CHPh and [PtLL′] fragments. In contrast to complexes of 1, 2, 4, 5, one-electron oxidation of 3 and 6 is reversible, indicating the greater electrochemical stability of lasts relative to of 1, 2, 4, 5.