Kinetics and mechanism of oxidation of nickel(II) tetraazamacrocycles by the peroxydisulphate anion in aqueous and binary aqueous mixtures

Abstract

The kinetics of oxidation of several nickel(II) tetraazamacrocycles by the peroxydisulphate anion have been studied in water and in binary aqueous mixtures. The reactions proceed via an ion-pairing pre-equilibrium, followed by metal ion-assisted peroxy-bond fissure within the ion-pair solvent shell. The derived rate law is[Formula: see text]Ion-pairing constants have been determined and have been found to be little influenced by steric factors, but do depend on solvent composition. Rate constants have been extracted using the rate expression and activation energies have been estimated from temperature dependences.