Rhodium Complexes in P-C Bond Formation: Key Role of a Hydrido Ligand

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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2021-01, Vol.143 (1), p.349-358
Main Authors: Varela-Izquierdo, Víctor, Geer, Ana M, Navarro, Janeth, López, José A, Ciriano, Miguel A, Tejel, Cristina
Format: Article
Language:English
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Summary: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(PMe )(PPh )] ( ), 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 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(PMe )(PPh )] as well as from stoichiometric and kinetic studies.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c11010