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Authors: Aurore Denjean, Ainara Nova, David Balcells.
Summary
The alkylation of amines with alcohols by borrowing hydrogen (BH) is a versatile synthetic route to various relevant compounds, including drugs and agrochemicals. The interest in single atom catalysts (SACs) combining the advantages of homogeneous and heterogeneous systems motivated this computational study on BH catalyzed by nickel SACs.
We found that the oxidation, charge, and spin states of the system, as well as the geometry of the support, all have a strong influence on the BH mechanism. The free energy of the catalyst reduction by molecular hydrogen was strongly correlated to its reactivity, thus being identified as a useful descriptor. Further, the mechanism followed an unusual reaction pathway in which the support takes and delivers hydrogen, with the metal playing a spectator role. This study provides useful insights for the further development of BH SACs.
Published: July 15th 2024. ACS Catal., 2024, 14, 11332–11342. https://pubs.acs.org/doi/10.1021/acscatal.4c02182