2026-06-07T18:58:44Zhttps://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

00925njm 22002777a 4500 dc Kalkuhl, Till author Fernández López, Israel author Hadlington, Terrance author 2025 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 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. 10.1016/j.chempr.2024.10.016 https://hdl.handle.net/20.500.14352/120252 https://doi.org/10.1016/j.chempr.2024.10.016 https://www.sciencedirect.com/science/article/pii/S2451929424005424 Cooperative hydrogenation catalysis at a constrained gallylene-nickel(0) interface