Coordination complexes of the tungsten(VI) oxide fluorides WOF4 and WO2F2 with neutral oxygen- and nitrogen-donor ligands

[WOF4(MeCN)], prepared from a 1:1 ratio of WF6 and O(SiMe3)(2) in MeCN, is a convenient synthon for the preparation of complexes of WOF4 and WO2F2 with neutral N- or O-donor ligands. It reacts with monodentate ligands L (L=OPPh3, OPMe3, dmso, py) in a 1:1 ratio to form [WOF4L], whilst reaction of [WOF4(MeCN)], O(SiMe3)(2) and L' (L'=OPPh3, py, pyNO, dmso) in 1:1:2 ratio affords [WO2F2L'(2)]. The synthesis of [WO2F2(L-L)] (L-L=Ph2P(O)CH2P(O)Ph-2 or 1,10-phenanthroline) are also described. Similar complexes with arsines, thio- or seleno-ethers are not formed by these routes. The complexes have been characterised by microanalysis, IR, H-1 and F-19{H-1} NMR spectroscopy, and X-ray crystal structures are reported for [WOF4(OPPh3)], [WO2F2(OPPh3)(2)], [WO2F2{Ph2P(O)CH2P(O)Ph-2}] and [WO2F2(pyNO)(2)]. (C) 2016 The Authors. Published by Elsevier B.V.