Kalkuhl, TillFernández López, IsraelHadlington, Terrance2025-05-202025-05-202025Kalkuhl, 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.2024.10.016.10.1016/j.chempr.2024.10.016https://hdl.handle.net/20.500.14352/120252The 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 transformationsengAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/journal articlehttps://doi.org/10.1016/j.chempr.2024.10.016https://www.sciencedirect.com/science/article/pii/S2451929424005424open access547Cooperative catalysisBimetallic catalysisHydrogen activationMetallo-ligandsGallylene ligandSmall molecule activationSustainable catalysisNovel mechanismsKinetic analysisReversible activationQuímica23 Química