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

Ziliang Yuan, Bo Han, Bing Liu, Jie Sun (), Peng Zhou, Rentao Mu () and Zehui Zhang ()
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Ziliang Yuan: South-Central Minzu University
Bo Han: China University of Geosciences
Bing Liu: South-Central Minzu University
Jie Sun: South-Central Minzu University
Peng Zhou: South-Central Minzu University
Rentao Mu: Chinese Academy of Sciences
Zehui Zhang: South-Central Minzu University

Nature Communications, 2025, vol. 16, issue 1, 1-13

Abstract: Abstract 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-Csp3-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-Csp3-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 (Ov) 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 Ov sites in MgO nanoclusters. Theoretical calculation further confirmed that Ov significantly lowered the energy barrier of the hydrogen atom transfer from α-Csp3-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.

Date: 2025
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DOI: 10.1038/s41467-025-58222-6

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