Electrochemical investigation of [Co4(μ3-O)4(μ-OAc)4(py)4] and peroxides by cyclic voltammetry

Abstract

Two oxidative redox processes of the neutral cobalt(III) cubane, [Co₄(μ₃-O)₄(μ-OAc)₄(py)₄], were investigated by cyclic voltammetry at a glassy carbon electrode in acetonitrile. In addition to the first quasi-reversible one-electron oxidation at E_1/2 = 0.283 V vs. Fc^0/+, a second quasi-reversible one-electron oxidation was observed at E_1/2 = 1.44 V vs. Fc^0/+. Oxidation at this potential does not facilitate water oxidation. In the presence of tert-butylhydroperoxide the peak current of this second oxidation increases, suggesting oxidation of the peroxide by the doubly oxidised cubane.