2026-06-08T02:38:26Zhttps://docta.ucm.es/rest/oai/request

oai:docta.ucm.es:20.500.14352/1202522025-05-21T18:31:31Zcom_20.500.14352_14col_20.500.14352_15

Cooperative hydrogenation catalysis at a constrained gallylene-nickel(0) interface Kalkuhl, Till Fernández López, Israel Hadlington, Terrance The discovery of unique mechanisms in 3d metal catalysis is of paramount importance in utilizing these Earth-abundant metals in place of scarce precious metals. Inspired by the Horiuti-Polanyi mechanism at play in heterogeneous hydrogenation catalysts, we describe a bimetallic molecular catalyst that can selectively semi-hydrogenate alkynes via a ligand-to-substrate hydride transfer mechanism. This mimics established heterogeneous mechanisms in which remote surface-bound hydride ligands undergo a similar reactive process. This is achieved through the development of a chelate-constrained gallium(I) ligand, which operates in concert with nickel(0) to (reversibly) cleave H2, generating a [GaNi] 1,2-dihydride complex that is found to be the resting state in the catalytic process. This discovery takes steps toward utilizing non-innocent low-valent group 13 centers in effective cooperative catalysis, opening new mechanistic pathways that may aid in employing Earth-abundant metals in key catalytic transformations 2025-05-20T10:16:56Z 2025-05-20T10:16:56Z 2025-05-20T10:16:56Z 2025 journal article https://hdl.handle.net/20.500.14352/120252 XXXX-XXXX 10.1016/j.chempr.2024.10.016 eng PID2022-139318NB-I00 101076897 RED2022-134331-T MICIU/AEI/10.13039/501100011033 Kalkuhl, Till L., et al. «Cooperative hydrogenation catalysis at a constrained gallylene-nickel(0) interface». Chem, vol. 11, n.o 4, abril de 2025, p. 102349. ScienceDirect, https://doi.org/10.1016/j.chempr.2024.10.016. http://creativecommons.org/licenses/by-nc-nd/4.0/ open access Attribution-NonCommercial-NoDerivatives 4.0 International Cell-Elsevier