Hydrogenation studies involving halobis(phosphine)-rhodium(I) dimers: Use of parahydrogen induced polarisation to detect species present at low concentration

Reaction of [RhCl(PPh(3))(2)](2) with parahydrogen revealed that the binuclear dihydride [Rh(H)(2)(PPh(3))(2)(mu-Cl)(2)Rh(PPh(3))(2)] and the tetrahydride complex [Rh(H)(2)(PPh(3))(2)(mu-Cl)](2) are readily formed. While magnetisation transfer from free H, into both the hydride resonances of the tetrahydride and [Rh(H)(2)Cl(PPh(3))(3)] is observable, neither transfer into [Rh(H)(2)(PPh(3))(2)(mu- Cl)(2)Rh(PPh(3))(2)] nor transfer between the two binuclear complexes is seen. Consequently [Rh(H)(2)(PPh(3))(2)(mu-Cl)](2) and [Rh(H)(2)(PPh(3))(2)(mu-Cl)(2)Rh(PPh(3))(2)] are not connected on the NMR timescale by simple elimination or addition of H(2). The rapid exchange of free H(2) into the tetrahydride proceeds via reversible halide bridge rupture and the formation of [Rh(H)(2)(PPh(3))(2)(mu- Cl)RhCl(H)(2)(PPh(3))(2)]. When these reactions are examined in CD(2)Cl(2), the formation of the solvent complex [Rh(H)(2)(PPh(3))(2)(mu-Cl)(2)Rh(CD(2)Cl(2))-(PPh(3))] and the deactivation products [Rh(Cl)(H)(PPh(3))(2)(mu-Cl)(mu-H)Rh(Cl)-(H)(PPh(3))(2)] and [Rh(Cl)(H)(CD(2)Cl(2))-(PPh(3))(2)(mu-Cl)(mu-H)Rh(Cl)(H)(PPh(3))(2)] is indicated. In the presence of an alkene and parahydrogen, signals corresponding to binuclear complexes of the type [Rh(H)(2)(PPh(3))(2)(mu-Cl)(2)(Rh)(PPh(3))(alkene)] are detected. These complexes undergo intramolecular hydride interchange in a process that is independent of the concentration of styrene and catalyst and involves halide bridge rupture, followed by rotation about the remaining Rh-Cl bridge, and bridge reestablishment. This process is facilitated by electron rich alkenes. Magnetisation transfer from the hydride ligands of these complexes into the alkyl group of the hydrogenation product is also observed. Hydrogenation is proposed to proceed via binuclear complex fragmentation and trapping of the resultant intermediate [RhCl(H)(2)(PPh(3))(2)] by the alkene. Studies on a number of other binuclear dihydride complexes including [(H)(Cl)Rh(PMe(3))(2)(mu-H)(mu-Cl)Rh-(CO)(PMe(3))], [(H)(2)Rh(PMe(3))(2)(mu-Cl)(2)-Rh(CO)(PMe(3))] and [HRh(PMe(3))(2)- (mu-H)(mu-Cl)(2)Rh(CO)(PMe(3))] reveal that such species are able to play a similar role in hydrogenation catalysis. When the analogous iodide complexes [RhI(PPh(3))(2)], and [RhI(PPh(3))(3)] are examined, [Rh(H)(2)(PPh(3))(2)(mu-I)(2)Rh-(PPh(3))(2)], [Rh(H)(2)(PPh(3))(2)(mu-I)](2) and [Rh(H)(2)I(PPh(3))(3)] are observed in addition to the corresponding binuclear alkene-dihydride products. The higher initial activity of these precursors is offset by the formation of the trirhodium phosphide bridged deactivation product, [{(H)(PPh(3))Rh(mu-H)(mu-I)(mu-PPh(2))Rh(H)(PPh(3))}(mu-I)(2)Rh(H)(2)(PPh(3))(2)].