Rhodium(III)-NSi Catalyzed Styrene Hydrosilylation: Evidence of the Hemilabile Character of NSi-Type Ligands

Gómez-España, Alejandra ; Padilla, Marina ; Martínez de Morentin, Aitor ; García-Orduña, Pilar ; Huertos, Miguel A. ; Munarriz, Julen (Universidad de Zaragoza) ; Fernández-Alvarez, Francisco J. (Universidad de Zaragoza)

Resumen: The 18e saturated rhodium(III) species [Rh(H)(X)(κ2‐NSitBu2)(bipyMe2)] (NSitBu2={4‐methylpyridine‐2‐yloxy}ditertbutylsilyl; bipyMe2=4,4'‐dimethylbipyridine) (X=Cl, 1; OTf, 2) have been prepared and characterized by NMR spectroscopy and in the case of 2 it has been possible to determine its solid‐state structure by X‐ray diffraction. Complex 1 has proven to be an effective catalyst precursor for the reaction of styrene derivatives with hydrosilanes in CD2Cl2. However, under catalytic conditions complex 2 decomposes. The performance of the 1‐catalyzed reaction of styrene with hydrosilanes strongly depends on the nature of the silane, the best catalytic performance was achieved using HSiMe2Ph. Theoretical and 1H NMR studies indicate that the hemilabile nature of the NSi ligand is key to understanding the catalytic activity of compound 1.

Idioma: Inglés

DOI: 10.1002/chem.202404657

Año: 2025

Publicado en: Chemistry - A European Journal 31, 13 (2025), e202404657 [9 pp.]
ISSN: 0947-6539

Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2023-148113OB-I00
Financiación: info:eu-repo/grantAgreement/ES/UZ/JIUZ-2023-CIE-10

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Física (Dpto. Química Física)