Reactions of tris-diimine and diimine-cyanide complexes of iron(II) with peroxoanions in solution

Investigations of the kinetics of reactions of low-spin iron(II)-diimine-cyanide complexes with peroxodiphosphate, peroxoborate and peroxomonosulphate suggested that only the last-named could act by rate-determining oxidation. Peroxodiphosphate and perborate react by rate-limiting dissociation with the subsequent rapid oxidation of the products of this dissociation. The reactivity trend for peroxomonosulphate oxidation of the [Fe(CN)4(bipy)]2− anion in water-acetonitrile mixtures is reported, and analysed into initial state and transition state contributions with the aid of appropriate assumptions.