Catalytic activation of remote alkenes through silyl-rhodium(iii) complexes
The tandem isomerization-hydrosilylation reaction is a highly valuable process able to transform mixtures of internal olefins into linear silanes. Unsaturated and cationic hydrido-silyl-Rh(iii) complexes have proven to be effective catalysts for this reaction. Herein, three silicon-based bidentate l...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/342719 |
| Acceso en línea: | http://hdl.handle.net/10261/342719 |
| Access Level: | acceso abierto |
| Palabra clave: | Catalyst activity Hydrosilylation Ligands Rhodium compounds Synthesis (chemical) X ray diffraction Bidentate ligands Catalytic activation Cationics Hydrosilylation reaction Hydrosilylations Isomerisation Rhodium complexes Silicon-based X- ray diffractions Olefins |
| Sumario: | The tandem isomerization-hydrosilylation reaction is a highly valuable process able to transform mixtures of internal olefins into linear silanes. Unsaturated and cationic hydrido-silyl-Rh(iii) complexes have proven to be effective catalysts for this reaction. Herein, three silicon-based bidentate ligands, 8-(dimethylsilyl)quinoline (L1), 8-(dimethylsilyl)-2-methylquinoline (L2) and 4-(dimethylsilyl)-9-phenylacridine (L3), have been used to synthesize three neutral [RhCl(H)(L)PPh] (1-L1, 1-L2 and 1-L3) and three cationic [Rh(H)(L)(PPh)][BAr] (2-L1, 2-L2 and 2-L3) Rh(iii) complexes. Among the neutral compounds, 1-L2 could be characterized in the solid state by X-ray diffraction showing a distorted trigonal bipyramidal structure. Neutral complexes (1-L1, 1-L2 and 1-L3) failed to catalyze the hydrosilylation of olefins. On the other hand, the cationic compound 2-L2 was also characterized by X-ray diffraction showing a square pyramidal structure. The unsaturated and cationic Rh(iii) complexes 2-L1, 2-L2 and 2-L3 showed significant catalytic activity in the hydrosilylation of remote alkenes, with the most sterically hindered (2-L2) being the most active one. |
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