Hydrogen Bond-Enabled Heterolytic and Homolytic Peroxide Activation within Nonheme Copper(II)-Alkylperoxo Complexes

To explore the reactivity of copper-alkylperoxo species enabled by the heterolytic peroxide activation, room-temperature stable mononuclear nonheme copper(II)-alkylperoxo complexes bearing a N-(2-ethoxyethanol)-bis(2picolyl)amine ligand (HN₃O₂), [Cu^II(OOR)(HN₃O₂)]⁺ (R = cumyl or ^tBu), were synthesized and spectroscopically characterized. A combined experimental and computational investigation on the reactivity and reaction mechanisms in the phosphorus oxidation, C-H bond activation, and aldehyde deformylation reactions by the copper(II)-alkylperoxo complexes has been conducted. DFT-optimized structures suggested that a hydrogen bonding interaction exists between the ethoxyethanol backbone of the HN₃O₂ ligand and either the proximal or distal oxygen atom of the alkylperoxide moiety, and this interaction consequently results in the enhanced stability of the copper(II)-alkylperoxo species. In the phosphorus oxidation reaction, both experimental and computational results indicated that a phosphine-triggered heterolytic O-O bond cleavage occurred to yield phosphine oxide and alcohol products. DFT calculations suggested that (i) the H-bonding between the ethoxyethanol backbone and distal oxygen of the alkylperoxide moiety and (ii) the phosphine binding to the proximal oxygen of the alkylperoxide moiety engendered the heterolytic peroxide activation. In the C-H bond activation reactions, temperature-dependent reactivity of the copper(II)-alkylperoxo complexes was observed, and a relatively strong activation energy of 95 kcal mol^-1 was required to promote the homolytic peroxide activation. A rate-limiting hydrogen atom abstraction reaction of xanthene by the putative copper(II)-oxyl radical resulted in the formation of the dimeric copper product and the substrate radical that further underwent autocatalytic oxidation reactions to form an oxygen incorporated product. Finally, amphoteric reactivity of copper(II)-alkylperoxo complexes has been assessed by conducting kinetic studies and product analysis of the aldehyde deformylation reaction.