Kinetics of peroxodisulphate oxidation of dicyanobis-(2,2′-bipyridyl)iron(II) and of the tetracyano-2,2′-bipyridylferrate(II) anion; initial state and transition state effects in reactions of tris-diimine and diimine-cyanide complexes of iron(II)

The rate law, rate constants, and activation parameters are reported for peroxodisulphate oxidation of the Fe(bipy) (CN)42− anion in aqueous solution. Rate constants are also reported for peroxodisulphate oxidation of Fe(bipy)(CN)42− and of Fe(bipy)2(CN)2 in various binary aqueous mixtures at 298.2 K. Solvent effects on reactivity in these oxidations and in dissociation of Fe(bipy)2(CN)2 and of Fe(phen)32+ are discussed in terms of initial state and transition state solvation effects and chemical potentials. Solvent effects on reactivity for Fe(bipy)32+ + 2CN− = Fe(bipy)2(CN)2 + bipy in aqueous methanol are analysed into initial state, transition state, and final state contributions.