Mechanistic Investigations on Hydrogenation, Isomerization and Hydrosilylation Reactions Mediated by a Germyl-Rhodium System
We recently disclosed a dehydrogenative double C−H bond activation reaction in the unusual pincer-type rhodium-germyl complex [(ArMes)2ClGeRh] (ArMes=C6H3-2,6-(C6H2-2,4,6-Me3)2). Herein we investigate the catalytic applications of this Rh/Ge system in several transformations, namely trans-semihydrog...
| 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:11441/162110 |
| Acceso en línea: | https://hdl.handle.net/11441/162110 https://doi.org/10.1002/cctc.202200157 |
| Access Level: | acceso abierto |
| Palabra clave: | Germanium Rhodium Semihydrogenatium Kinetic studies Tandem catalysis |
| Sumario: | We recently disclosed a dehydrogenative double C−H bond activation reaction in the unusual pincer-type rhodium-germyl complex [(ArMes)2ClGeRh] (ArMes=C6H3-2,6-(C6H2-2,4,6-Me3)2). Herein we investigate the catalytic applications of this Rh/Ge system in several transformations, namely trans-semihydrogenation of internal alkynes, trans-isomerization of olefins and hydrosilylation of alkynes. We have compared the activity and selectivity of this catalyst against other common rhodium precursors, as well as related sterically hindered rhodium complexes, being the one with the germyl fragment superior in terms of selectivity towards E-isomers. To increase this selectivity, a tandem catalytic protocol that incorporates the use of a heterogeneous catalyst for the trans-semihydrogenation of internal alkynes has been devised. Kinetic mechanistic investigations provide important information regarding the individual catalytic cycles that comprise the overall trans-semihydrogenation of internal alkynes. |
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