Catalytic decomposition of dimethyldioxirane and cyclic acetone triperoxide in presence of polynuclear complexes of cobalt(II,III) and copper(II)

Dinuclear copper and cyclic trinuclear cobalt complexes with pyrazolate and OH− bridges are able to decompose dimethyldioxirane in acetone, triggering radical reactions. Some products of reactions between organic substrates (cyclohexene or ethylbenzene) or acetone with secondary radicals formed from dimethyldioxirane: hydroxyl, methyl and acetomethyl, were identified and quantified. Tested complexes were also able to homolytically decompose cyclic acetone triperoxide and the radicals formed induced homolytic oxidation of cyclohexene producing 2-cyclohexen-1-ol and 2-cyclohexen-1-one at moderate yield.

Graphical abstractDimethyldioxirane and cyclic acetone triperoxide decompose in presence of polynuclear complexes of copper(II) and cobalt(II,III). The oxygen from these oxidants was found in products of oxidation of cyclohexene. The complexes trigger also the radical pathway of decomposition of dimethyldioxirane with hydroxyl, methyl and acetomethyl radicals involved. Figure optionsDownload full-size imageDownload as PowerPoint slide