Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis
The incorporation of boron functionalities into transition-metal catalysts has become a promising strategy to improve catalytic performance, although their synthesis typically entails the preparation of sophisticated bifunctional ligands. We report here the facile and direct postsynthetic functional...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/157966 |
| Acceso en línea: | https://hdl.handle.net/11441/157966 https://doi.org/10.1021/acscatal.3c02764 |
| Access Level: | acceso abierto |
| Palabra clave: | Hydrogenation Ligand functionalization Pendant borane Rhodium σ-borane complex |
| Sumario: | The incorporation of boron functionalities into transition-metal catalysts has become a promising strategy to improve catalytic performance, although their synthesis typically entails the preparation of sophisticated bifunctional ligands. We report here the facile and direct postsynthetic functionalization of rhodium(I) compound [(η5-C9H7)Rh(PPh3)2] (1) by treatment with perfluorinated boranes. Borane addition to 1 results in an unusual C(sp2)-H hydride migration from the indenyl ligand to the metal with the concomitant formation of a C-B bond. In the case of Piers’ borane [HB(C6F5)2], this is followed by a subsequent hydride migration that leads to an unprecedented 1,2-hydrogen shift reminiscent of Milstein’s cooperative dearomatization pathways. Computational investigations provide a mechanistic picture for the successive hydride-migration steps, which enriches the non-innocent chemistry of widespread indenyl ligands. Moreover, we demonstrate that the addition of Piers’ borane is highly beneficial for catalysis, increasing catalyst efficiency up to 3 orders of magnitude. |
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