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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 547 Cooperative catalysis Bimetallic catalysis Hydrogen activation Metallo-ligands Gallylene ligand Small molecule activation Sustainable catalysis Novel mechanisms Kinetic analysis Reversible activation Química 23 Química 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 Fondo de la industria química (FCI) Universidad de Munich Depto. de Química Orgánica Fac. de Ciencias Químicas TRUE pub 2025-05-20T10:16:56Z 2025-05-20T10:16:56Z 2025 journal article VoR 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. Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ open access application/pdf Cell-Elsevier