Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes

Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, Co^III(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R'H) at ambient conditions (Co^III(qpy)OOR + R'H → Co^II(qpy) + R'^• + ROOH). The resulting alkyl radical (R'^•) reacts rapidly with O₂ to form alkylperoxy radical (R'OO^•), which is efficiently scavenged by Co^II(qpy) to give Co^III(qpy)OOR' (Co^II(qpy) + R'OO^• → Co^III(qpy)OOR'). This unique reactivity enables Co^III(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R'H + O₂ → R'OOH) under 1 atm air and at room temperature.