Electron-transfer reactions of benzene-1,2-diols with hexachloroiridate(IV) in acidic perchlorate media

Abstract

The kinetics of oxidation of a series of benzene-1,2-diols by hexachloroiridate(IV) have been investigated by the stopped-flow technique in aqueous acidic perchlorate media. The reactions are first order in the concentrations of both reactants and independent of acidity and added [IrCl₆]^3–. The experimental results are discussed in the light of Marcus theorywith reference to previous findings on the kinetic behaviour of benzene-1,4-diols. The dependence of the free energies of activation on the free energies of reaction provides information on the mechanism of these non-complementary redox reactions.