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.
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