Rhodium complexes in p-C bond formation: Key role of a hydrido ligand
Resumen: Olefin hydrophosphanation is an attractive route for the atom-economical synthesis of functionalized phosphanes. This reaction involves the formation of P-C and H-C bonds. Thus, complexes that contain both hydrido and phosphanido functionalities are of great interest for the development of effective and fast catalysts. Herein, we showcase the excellent activity of one of them, [Rh(Tp)H(PMe3)(PPh2)] (1), in the hydrophosphanation of a wide range of olefins. In addition to the required nucleophilicity of the phosphanido moiety to accomplish the P-C bond formation, the key role of the hydride ligand in 1 has been disclosed by both experimental results and DFT calculations. An additional Rh-H··· C stabilization in some intermediates or transition states favors the hydrogen transfer reaction from rhodium to carbon to form the H-C bond. Further support for our proposal arises from the poor activity exhibited by the related chloride complex [Rh(Tp)Cl(PMe3)(PPh2)] as well as from stoichiometric and kinetic studies.
Idioma: Inglés
DOI: 10.1021/jacs.0c11010
Año: 2021
Publicado en: Journal of the American Chemical Society 143, 1 (2021), 349-358
ISSN: 0002-7863

Financiación: info:eu-repo/grantAgreement/ES/AEI-FEDER/CTQ2017-83421-P
Financiación: info:eu-repo/grantAgreement/ES/DGA-FEDER/E08-17R
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/FPI fellowship
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/Jdc contract
Tipo y forma: Artículo (PostPrint)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)

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