Dicoordinate Au(I)−Ethylene Complexes as Hydroamination Catalysts
A series of gold(I)–ethylene π-complexes containing a family of bulky phosphine ligands has been prepared. The use of these sterically congested ligands is crucial to stabilize the gold(I)–ethylene bond and prevent decomposition, boosting up their catalytic performance in the highly underexplored hy...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2022 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/182118 |
| Acceso en línea: | https://hdl.handle.net/11441/182118 https://doi.org/10.1021/acscatal.1c05823 |
| Access Level: | acceso abierto |
| Palabra clave: | Gold catalysis π-complexes Ethylene functionalization Hydroamination Bulky phosphines |
| Sumario: | A series of gold(I)–ethylene π-complexes containing a family of bulky phosphine ligands has been prepared. The use of these sterically congested ligands is crucial to stabilize the gold(I)–ethylene bond and prevent decomposition, boosting up their catalytic performance in the highly underexplored hydroamination of ethylene. The precatalysts bearing the most sterically demanding phosphines showed the best results reaching full conversion to the hydroaminated products under notably mild conditions (1 bar of ethylene pressure at 60 °C). Kinetic analysis together with density functional theory calculations revealed that the assistance of a second molecule of the nucleophile as a proton shuttle is preferred even when using an extremely congested cavity-shaped Au(I) complex. In addition, we have measured a strong primary kinetic isotopic effect that is consistent with the involvement of X–H bond-breaking events in the protodeauration turnover-limiting step. |
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