Homolytic decomposition of cumyl hydroperoxide under the action of zinc, cadmium, and mercury 2-ethylhexanoates

The free-radical decomposition of cumyl hydroperoxide (CHP) and the overall CHP decomposition process proceed via the same mechanism with similar kinetic parameters through the formation of a hydroperoxide-metal compound intermediate. The catalytic activity of metal ethylhexanoates decreases in the order Cd > Zn > Hg. The complex formation thermodynamics and decomposition kinetics are correlated with the metal ionization potentials, which are the lowest for cadmium. The zinc-family metals are catalytically more active than the Group IIA metals owing to their polarization effect. Within Group IIA, the catalytic properties are mainly determined by the nature of the interaction in the intermediate complex.