Tungsten(VI) and tungsten(V) fluoride complexes.

WF6 reacts with phosphines R3P forming 1:1 compounds. With R=P(CH3)(3) the coordination around the tungsten atom is capped trigonal prismatic, with R=P(CH3)(2)C6H5 the coordination is capped octahedral, as established by single-crystal structure determinations: [(CH3)(3)P-WF6]: a= 752.5(21), b = 945.7(24) c=629.8(18) pm. beta=110.36(13)degrees, space group Cm, Z=2, [(CH3)(2)(C6H5)P-WF6]: a=762.2(2), b=1123.5(2), c= 2647.5(6) pm, space group Pbca, Z = 8. [(CF3CH2)(2)N-WF5] reacts smoothly With P(C6H5)(3) forming known P-(C6H5)(3)(F)(2) and [(CF3CH2)(2)N-WF4-P-(C6H5)(3)], a stable, green, molecular species, identified among other methods with an crystal structure determination: a=914.9(1), b=956.0(1), c= 1449.8(2) pm, alpha = 7.642(4), beta=81.648(3), gamma=81.519 degrees, space group P (1) over bar Z=2.