Atomically Dispersed N/O-Coordinated Cobalt Catalyst Enables Aerobic Oxygenation of Olefins under Ambient Conditions

Abstract

Oxygenation of hydrocarbons with O2 as the oxidant is industrially important; however, current processes typically require high temperature and/or pressure. Herein, we report an atomically dispersed Co catalyst (Co1/NOC) capable of converting olefins to corresponding ketones and alcohols under ambient conditions with high activity and chemoselectivity. Isotopic labeling and intermediate trapping experiments reveal that reactions proceed via a heterogeneous hydrogen atom transfer (HAT) mechanism with carbon-centered radicals, followed by activating molecular oxygen. Co1/NOC surpasses homogeneous Co-based HAT catalysts in activity, showing that the properly doped carbon support could provide a suitable coordinating environment. The turnover frequency of Co1/NOC is more than three times higher than that of Co1/NC, which is attributed to the downshift d-band center of the cobalt center due to the extra O-coordination in the Co1/NOC. Furthermore, Co1/NOC is able to catalyze the oxygenation of styrene derivatives with sensitive functional groups, achieving selective oxygenation of the carbon–carbon double bond.