SYNTHESIS AND CHARACTERIZATION OF THE HETEROMETALLIC PHOSPHINIDENE CLUSTERS (C5ME5)WRU3(CO)10(MU-3-H)(MU-3-PPH), (C5H5)WRU2(CO)8(MU-H)(MU-3-PPH), AND (C5ME5)WRU2(CO)8(MU-H)(MU-3-PPH)

[[abstract]]Reaction of Ru3(CO)10(mu-H)(mu-PPh2) with an excess of tungsten hydrides LW(CO)3H, L = Cp* and Cp, in refluxing toluene produced heterometallic phosphinidene cluster complexes Cp*WRu3(CO)10(mu-3-H)(mu-3-PPh) (1) and CpWRu2-(CO)8(mu-H)(mu-3-PPh) (2), respectively. Tetranuclear complex 1 has been identified as an intermediate to the trinuclear complex, because heating of 1 under carbon monoxide in refluxing toluene induced a cluster fragmentation, giving an analogous phosphinidene derivative Cp*WRu2(CO)8(mu-H)(mu-3-PPh) (3) in 72% yield. The structures of all three complexes were determined by X-ray diffraction. Complex 1 adopts a tetrahedral framework with a phosphinidene capping a WRu2 face and a hydride associated with the adjacent WRu2 face, whereas complexes 2 and 3 possess a triply bridging phosphinidene ligand and differ from each other by the location of the edge-bridging hydride ligand. In accordance with structural diversity in the solid state, complex 3 is present as two isomers in solution via rapid hydride migration. Crystal data for 1: space group P2(1)/c, a = 9.813 (3) angstrom, b = 18.253 (4) angstrom, c = 18.463 (3) angstrom, beta = 93.730 (18)-degrees, Z = 4, final R = 0.026, R(w) = 0.025 for 3750 reflections with I > 2-sigma(I). Crystal data for 2: space group P1BAR, a = 9.3411 (23) angstrom, b = 10.2931 (14) angstrom, c = 12.635 (3) angstrom, alpha = 85.716 (15)-degrees, beta = 73.743 (20)-degrees, gamma = 73.013 (14)-degrees, Z = 2, final R = 0.030, R(w) = 0.035 for 3659 reflections with I > 2-sigma(I). Crystal data for 3: space group Cc, a = 9.711 (2) angstrom, b = 17.800 (3) angstrom , c = 32.398 (3) angstrom, beta = 90.697 (22)-degrees, Z = 8, final R = 0.034, R(w) = 0.035 for 4487 reflections with I > 2-sigma(I).[[fileno]]2010302010106[[department]]化學