Snapshots of Cooperative Trimetallic Alkene Hydrogenation

Bimetallic 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 f...

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Detalles Bibliográficos
Autores: Fernández, I,, Hadlinton, T. J., Kalkuhl, T. L.
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/131544
Acceso en línea:https://hdl.handle.net/20.500.14352/131544
Access Level:acceso abierto
Palabra clave:54
Catalytic reactions
Hydrocarbons
Hydrogenation
Ligands
Metals
Química
23 Química
Descripción
Sumario:Bimetallic 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.