Nucleophilic reactivity of a mononuclear cobalt(III)–bis(tert-butylperoxo) complex

A mononuclear cobalt(III)–bis(tert-butylperoxo) adduct (Co^III–(OO^tBu)₂) bearing a tetraazamacrocyclic ligand was synthesized and characterized using various physicochemical methods, such as X-ray, UV-vis, ESI-MS, EPR, and NMR analyses. The crystal structure of the Co^III–(OO^tBu)₂ complex clearly showed that two OO^tBu ligands bound to the equatorial position of the cobalt(III) center. Kinetic studies and product analyses indicate that the Co^III–(OO^tBu)₂ intermediate exhibits nucleophilic oxidative reactivity toward external organic substrates.