Reactions of tungsten hexafluoride with sulphite esters and with trimethyl phosphite. Preparation and reactions of alkoxy- and phenoxytungsten (VI) pentafluorides

Abstract

Tungsten hexafluoride reacts with dimethyl, diethyl, and diphenyl sulphites to give the corresponding alkoxy- or phenoxy-tungsten(VI) pentafluoride, ROWF₅, and the fluorosulphite ester, ROS(O)F. MeOWF₅ and PhOWF₅ are stable at 20°, but EtOWF₅ decomposes to give WOF₄ and EtF. MeOWF₅ and (MeO)₂PF are the initial products from the reaction of WF₆ with trimethyl phosphite but subsequent reactions occur to give [(MeO)₃PMe]+[WOF₅]^–, (MeO)₂P(O)Me, (MeO)(F)P(O)Me, MeP(O)F₂, and WOF₄,OP(OMe)₂Me. The products obtained depend on the reaction conditions. Structures for the tungsten–fluorine compounds are suggested from their ¹H and ¹⁹F n.m.r. spectra and the reactions of MeOWF₅ with (MeO)₃P, C₆H₆, and C₅H₅N are reported.