Fluoride-ion acceptor properties of WSF 4: Synthesis, characterization, and computational study of the WSF _5 - and W _2S _2F _9 - anions and 19F NMR spectroscopic characterization of the W _2OSF _9 - anion

摘要

The new [N(CH _3) _4][WSF _5] salt was synthesized by two preparative methods: (a) by reaction of WSF _4 with [N(CH _3) _4][F] in CH _3CN and (b) directly from WF _6 using the new sulfide-transfer reagent [N(CH _3) _4][SSi(CH _3) _3]. The [N(CH _3) _4][WSF _5] salt was characterized by Raman, IR, and ~(19)F NMR spectroscopy and [N(CH _3) _4][WSF _5]CH _3CN by X-ray crystallography. The reaction of WSF _4 with half an aliquot of [N(CH _3) _4][F] yielded [N(CH _3) _4][W _2S _2F _9], which was characterized by Raman and ~(19)F NMR spectroscopy and by X-ray crystallography. The WSF _5 - and W _2S _2F _9 - anions were studied by density functional theory calculations. The novel [W _2OSF _9] - anion was observed by ~(19)F NMR spectroscopy in a CH _3CN solution of WOF _4 and WSF _5 -, as well as CH _3CN solutions of WSF _4 and WOF _5 -.