Copper(II)−Hydroperoxo Complex Induced Oxidative N-Dealkylation Chemistry

A significant oxidative N-demethylation reaction occurs from a hydroperoxo−copper(II) species when formed within a tripodal tetradentate ligand framework possessing a pendant dimethylamine substrate. This mimics the monoxygenase activity occurring in the copper enzyme PHM. Observation of a product-based alkoxide−Cu intermediate and determination of a reaction kinetic isotope effect (kH/kD(intra) ∼ 2.3) by studying the ligand−N(CH3)(CD3) substrate provide further insights. The mononuclear CuII(-OOH) entity or species derived from this can promote biomimetic reactivity and thus requires further attention in biological or synthetic mechanistic studies.