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

• DOI: 10.1021/jacs.0c11010
• Publication Date: 2020-12-24T20:57:27Z
• Authors: Víctor Varela-Izq...; Ana M. Geer; Janeth Navarro; José A. López; Miguel A. Ciriano; Cristina Tejel
• Keywords: Moiety; Reductive elimination

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