The pressure dependence of rates of homolytic fission of metal–ligand bonds in aqueous solution

Abstract

The volume of activation for the exclusively homolytic decomposition of protonated 4-pyridylmethylchromium(III) ion in aqueous HClO4 at 63.4 °C is +19 cm3 mol−1, with negligible dependence on pressure up to 350 MPa at least. The origins of the strongly positive volumes of activation that characterize homolysis of complex cations in aqueous solution are examined.