Flash photolysis studies of charge-transfer photochemistry of nickel(II) and cobalt(III) complexes

Abstract

The photochemical behavior of cobalt(III) and nickel(II) complexes on excitation in the charge-transfer bands is reviewed in this article with particular reference to the study of intermediates. Investigations on the photoredox reactions of cobalt(III) and nickel(II) complexes using flash kinetic spectroscopic methods reveal details on the characteristics of the intermediates produced from the charge-transfer excited states of these metal complexes. The reactive species produced on photolysis of cobalt(III)-amine complexes activate molecular oxygen, producing mononuclear and dinuclear dioxygen species coordinated as superoxo and peroxo forms. Cobalt(III)-amino-acid complexes on photolysis lead to the formation of cobalt(III)-alkyl complexes which are identified as transients. The spectra and the decay kinetics are described with the view to elucidate mechanistic details. Nickel(II) macrocyclic complexes on excitation in the charge-transfer bands lead to oxidation of the metal centre. Scavenging experiments using dioxygen, alcohols and acids were carried out to understand the mechanistic details.