Tungsten(VI) and Tungsten(V) Fluoride Complexes

WF 6 reacts with phosphines R 3 P forming 1:1 compounds. With R=P(CH 3 ) 3 the coordination around the tungsten atom is capped trigonal prismatic, with R=P(CH 3 ) 2 C 6 H 5 the coordination is capped octahedral, as established by single‐crystal structure determinations: [(CH 3 ) 3 PWF 6 ]: a =752.5(21), b =945.7(24), c =629.8(18) pm. β =110.36(13)°, space group Cm , Z =2; [(CH 3 ) 2 (C 6 H 5 )PWF 6 ]: a =762.2(2), b =1123.5(2), c =2647.5(6) pm, space group Pbca , Z =8. [(CF 3 CH 2 ) 2 NWF 5 ] reacts smoothly with P(C 6 H 5 ) 3 forming known P(C 6 H 5 ) 3 (F) 2 and [(CF 3 CH 2 ) 2 NWF 4 P(C 6 H 5 ) 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, α =7.642(4), β =81.648(3), γ =81.519°, space group P $\bar 1$ , Z =2.