Electrochemistry of dinuclear, thiolato-bridged transition-metal compounds. Part 1. Electrochemical behaviour of [(η5-C5H5)(CO)3M(µ-SR)W(CO)5](R = Me, M = Mo or W; R = Ph, M = W) complexes in non-aqueous media

Abstract

The compounds [(η⁵-C₅H₅)(CO)₃M(µ-SR)W(CO)₅] have been studied by usual electrochemical methods (cyclic voltammetry, controlled-potential electrolysis, and coulometry). They undergo a destructive two-electron reduction according to an electrochemical–chemical–electrochemical process with a diffusion-controlled intervening chemical step. The [W(CO)₅(SMe)]^– anion generated by the reduction of the complexes undergoes chemical reactions leading to the dinuclear species [W₂(CO)₁₀(µ-SMe)]^– on the time-scale of controlled-potential electrolyses.