Mononuclear copper-alkylperoxo complexes in stoichiometric and catalytic reactions

Abstract

Mononuclear transition metal alkylperoxo complexes are important in diverse biological and catalytic oxidation processes. Among them, a number of Cu(II)-alkylperoxo species have been characterized and some of these complexes served as models of lipid peroxidation. Herein, we report the first example of Cu(II)-alkylperoxo complexes that affect aldehyde deformylation with an oxidative nucleophilic character and the kinetics of aldehyde deformylation by Cu(II)-alkylperoxo species at low temperature. The mononuclear Cu(II)-alkylperoxo complexes are characterized by various physicochemical methods such as UV-vis, CSI-MS, resonance Raman and EPR. Particularly, EPR data clearly exhibit tetragonal geometry of Cu(II)-alkylperoxo complexes, which was in good agreement with the results of DFT calculations. Interestingly, the Cu(II)-alkylperoxo complexes exhibit different reactivity at higher temperature, where the Cu(II)-alkylperoxo complexes are capable of catalyzing C-H bond activation (i.e., electrophilic reaction).