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'(center dot) + ROOH). The resulting alkyl radical (R'(center dot)) reacts rapidly with O-2 to form alkylperoxy radical (R'OO center dot), which is efficiently scavenged by Co-II(qpy) to give Co-III(qpy)OOR' (Co-II(qpy) + R'OO center dot -> Co-III(qpy)OOR'). This unique reactivity enables Co-III(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R' H + O-2 -> R'OOH) under 1 atm air and at room temperature.

Automated summary

The study introduces a new series of cobalt complexes that function as efficient catalysts for aerobic peroxidation of hydrocarbons at room temperature, offering a potential solution to the challenge of room temperature aerobic oxidation of hydrocarbons.