Electron-transfer reactions in non-aqueous media. VII. Reduction of CoF(NH₃)₅²⁺ and Co(HCOO)(NH₃)₅²⁺ by copper(I) in dimethyl sulfoxide-water mixtures

Abstract

Previous work on the reduction of a series of cobalt(III) complexes by iron(II) in dipolar aprotic solvents and in aqueous mixtures has been extended to reduction by copper(I). The greater stability of copper(I) to disproportionation in these media has permitted the study of the reduction of CoF(NH₃)₅²⁺ and Co(HCOO)(NH₃)₅²⁺ in range of solvents over a number of temperatures with a precision not possible in previous studies in water.

The results are consistent with an inner-sphere mechanism in which the copper(I) reductant is preferentially solvated by dimethyl sulfoxide to the exclusion of water in mixed solvents.