Catalytic hydrodechlorination of benzyl chloride promoted by Rh–N-heterocyclic carbene catalysts
The rhodium(I) complexes [Rh(Cl)(COD)(R-NHC-(CH2)3Si(OiPr)3)] [COD=cyclooctadiene; R=2,6-diisopropylphenyl (1 a); n-butyl (1 b)] are effective catalyst precursors for the homogeneous hydrodechlorination of benzyl chloride using HSiEt3 as hydrogen source. This reaction is selective to the formation o...
| Autores: | , , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2014 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/108734 |
| Acceso en línea: | http://hdl.handle.net/10261/108734 |
| Access Level: | acceso abierto |
| Palabra clave: | Heterogeneous catalysis Homogeneous catalysis Hydrodechlorinatio |
| Sumario: | The rhodium(I) complexes [Rh(Cl)(COD)(R-NHC-(CH2)3Si(OiPr)3)] [COD=cyclooctadiene; R=2,6-diisopropylphenyl (1 a); n-butyl (1 b)] are effective catalyst precursors for the homogeneous hydrodechlorination of benzyl chloride using HSiEt3 as hydrogen source. This reaction is selective to the formation of toluene. However, in presence of a stoichiometric amount of potassium tert-butoxide (KtBuO) the formation of mixtures containing toluene together with 17–19 mol % of the CC homocoupling product, namely PhCH2CH2Ph, is observed. A mechanism proposal based on experimental insights and theoretical calculations at the DFT level that allows explanation of the experimental findings is included. Moreover, the heterogeneous catalytic system based on catalyst 1 a supported on MCM-41 has been demonstrated to be effective for the solvent-free hydrodechlorination of benzyl chloride using HSiEt3 and HSiMe(OSiMe3)2. |
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