Catalytic carbon–chlorine bond cleavage via electrochemical reduction of [ReCl6]2–*

Abstract

Electrochemical reduction of hexachlororhenate(IV) in chlorinated solvents gave rise to a catalytic cycle producing free chloride and radical dimerisation products. Chlorine-36 tracer experiments showed this free chloride to be derived not from the solvent, as would be expected for a classical redox catalysis, but from the metal complex. A co-ordinatively unsaturated rhenium(III) intermediate capable of abstracting chlorine atoms to regenerate the starting material is proposed as the reactive species.