Fernández, I,Hadlinton, T. J.Kalkuhl, T. L.2026-02-052026-02-052025-12-05J. Am. Chem. Soc. 2025, 147, 46373−4638310.1021/jacs.5c15492https://hdl.handle.net/20.500.14352/131544Bimetallic cooperativity and synergistic effects have emerged as powerful tools that can enhance the reactivity and selectivity of catalytic systems, offering a pathway toward the development of catalysts based on Earth-abundant elements. Although not uncommon in nature, discrete molecular systems featuring more than two cooperative metal sites are virtually unknown. Herein we report the design of a well-defined molecular heterotrimetallic [Ga2Ni] system, which is effective in alkene hydrogenation catalysis. Species representing ‘snapshots’ of the catalytic cycle are isolated through consecutive addition of ethylene and dihydrogen, allowing for in-depth experimental mechanistic elucidation of two sequential 2-electron oxidative processes. Alongside combined computational, kinetic, and isotopic labeling studies, these findings reveal a fully mapped hydrogenation mechanism in which all three metal sites partake in the alkene hydrogenation process. This system thus provides unique insights into cooperative molecular multimetallic catalysis and establishes a blueprint for rationally designed multicentered cooperativity beyond established diatomic concepts.engjournal articlehttps://pubs.acs.org/doi/10.1021/jacs.5c15492open access54Catalytic reactionsHydrocarbonsHydrogenationLigandsMetalsQuímica23 Química