Rhodium Complexes in P–C Bond Formation: Key Role of a Hydrido Ligand
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https://figshare.com/articles/dataset/Rhodium_Complexes_in_P_C_Bond_Formation_Key_Role_of_a_Hydrido_Ligand/13488497
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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.
创建时间：
2020-12-24
