Mechanistic Insights on the β-(Z) alkyne hydrosilylation by a NHC-based Cp*Rh(III) catalyst: from catalyst design to an alternative model for H-Si activation
Poves-Ruiz, Isabel ; Sánchez-Page, Beatriz ; Jiménez, M. Victoria ; Gallegos, Miguel ; Munarriz, Julen (Universidad de Zaragoza) ; Passarelli, Vincenzo ; Pérez-Torrente, Jesús J. (Universidad de Zaragoza)
Resumen: In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI {(MeIm)2CH2}]+, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI2(IMe)] (IMe = 1,3-dimethylimidozol-2-ylidene). This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η4 -Cp*H], formed through protonation of the Cp* moiety.
Idioma: Inglés
DOI: 10.1016/j.jcat.2026.116721
Año: 2026
Publicado en: Journal of Catalysis 456 (2026), 116721 [13 pp.]
ISSN: 0021-9517
Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIU/PID2024-159030NA-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00
Tipo y forma: Article (Published version)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Física (Dpto. Química Física)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes.
Exportado de SIDERAL (2026-02-23-14:54:33)
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Idioma: Inglés
DOI: 10.1016/j.jcat.2026.116721
Año: 2026
Publicado en: Journal of Catalysis 456 (2026), 116721 [13 pp.]
ISSN: 0021-9517
Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIU/PID2024-159030NA-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00
Tipo y forma: Article (Published version)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Física (Dpto. Química Física)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. Exportado de SIDERAL (2026-02-23-14:54:33)
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Record created 2026-02-23, last modified 2026-02-23