Electron-transfer reactions of cobaloximes: kinetics and mechanisms of the vanadium(II) reduction of diammine-, amminebromo-, and amminechloro-bis(dimethylglyoximato)cobalt(III)

Abstract

The kinetics of the title reactions have been studied and their activation parameters and rate laws at 25 °C determined. It is concluded from these that the monohalogeno-complexes react by an outer-sphere mechanism while the reaction of the diammine complex is a substitution-controlled inner-sphere process. It is suggested that the reaction of Cr²⁺(aq) with the latter complex proceeds also by an inner-sphere mechanism.