Artículo
Rhodium(I) Complexes with Ligands Based on N-Heterocyclic Carbene and Hemilabile Pyridine Donors as Highly E Stereoselective Alkyne Hydrosilylation Catalysts
Autor/es | Morales Cerón, Judith
Lara Muñoz, Patricia López Serrano, Joaquín López Santos, Laura Salazar Pereda, Verónica Álvarez González, Eleuterio Suárez Escobar, Andrés Luis |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2017 |
Fecha de depósito | 2023-01-27 |
Publicado en |
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Resumen | Cationic rhodium(I) complexes containing picolyl-NHC
(NHC = N-heterocyclic carbene) ligands that differ in the substitution at
the 6-position of the pyridine donor serve as efficient E-selective alkyne
hydrosilylation ... Cationic rhodium(I) complexes containing picolyl-NHC (NHC = N-heterocyclic carbene) ligands that differ in the substitution at the 6-position of the pyridine donor serve as efficient E-selective alkyne hydrosilylation catalyst precursors. Particularly, when the steric hindrance of the picolyl fragment is increased, a catalyst precursor exhibiting high catalytic activities (TOF up to 500 h−1 at S/C ratios of 1000) and excellent E selectivities (E/α ratio ≥95/5) in the hydrosilylation of a series of aryl, alkyl, and functionalized terminal alkynes with both carbo- and alkoxysilanes has been obtained. The picolyl-NHC ligands in the Rh complexes exhibit a dynamic behavior in solution due to the hemilabile coordination of the pyridine fragment. Preliminary mechanistic studies support the involvement of Rh silyl hydrido species, which are generated in low concentrations from Rh complexes and the silane, in the hydrosilylation of alkynes in agreement with the assumption of Chalk−Harrod-type mechanisms. |
Agencias financiadoras | Ministerio de Economía y Competitividad (MINECO). España European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER) |
Identificador del proyecto | CTQ2013-45011-P
CTQ2016-80814-R CTQ2016-81797-REDC |
Cita | Morales Cerón, J., Lara Muñoz, P., López Serrano, J., López Santos, L., Salazar Pereda, V., Álvarez González, E. y Suárez Escobar, A.L. (2017). Rhodium(I) Complexes with Ligands Based on N-Heterocyclic Carbene and Hemilabile Pyridine Donors as Highly E Stereoselective Alkyne Hydrosilylation Catalysts. Organometallics, 36 (13), 2460-2469. https://doi.org/10.1021/acs.organomet.7b00361. |
Ficheros | Tamaño | Formato | Ver | Descripción |
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acs.organomet.7b00361.pdf | 1.812Mb | [PDF] | Ver/ | |