Unexpected activity of MgO nanoclusters for the reductive-coupling synthesis of organonitrogen chemicals with C = N bonds

Reductive-coupling of nitro compounds and alcohols is a sustainable route for constructing C = N bonds in organonitrogen chemicals, yet challenging due to the inertness of α-C sp3 -H bond in alcohols and the vulnerability of C = N bonds towards hydrogenation. Here, we report the surprising catalytic activity of ultrafine alkaline-earth metal oxide MgO nanoclusters (0.9 ± 0.3 nm) that efficiently activate α-C sp3 -H bonds, facilitating the transfer hydrogenation and synthesis of value-added chemicals bearing C = N bonds with high to excellent yields (86–99%). Controlled experiments and characterizations showed the crucial role of oxygen vacancies (O v ) and local Mg environment (Mg-O bond) in MgO for substrate adsorption and activation via electronic interactions between substrate’s negatively charged oxygen atoms and O v sites in MgO nanoclusters. Theoretical calculation further confirmed that O v significantly lowered the energy barrier of the hydrogen atom transfer from α-C sp3 -H in ethanol to the nitro group in nitrobenzene (29.3 vs . 52.9 kcal/mol), which is the rate-determining step with the highest energy barrier in reductive-coupling reactions. Our method not only provides an efficient and sustainable pathway for synthesizing organonitrogen chemicals with C = N bonds but also inspires the exploration of main group element catalysts as alternatives to transition metal and noble metal catalysts for organic transformations.