Convenient preparative routes to fluorido[(pentafluorophenyl)imido]tungstate(VI) salts have been developed. The reaction of WF₆·NC₅H₅ or [N(CH₃)₄][WF₇] with C₆F₅NH₂ results in quantitative formation of the C₅H₅NH⁺ or N(CH₃)₄⁺ salt of the W(NC₆F₅)F₅^– anion, respectively. The dissolution of [C₅H₅NH][W(NC₆F₅)F₅] in anhydrous HF results in the formation of [C₅H₅NH][W₂(NC₆F₅)₂F₉]. These salts have been comprehensively characterized in the solid state by X-ray crystallography and Raman spectroscopy and in solution by ¹⁹F and ¹H NMR spectroscopy. The crystal structures of the W(NC₆F₅)F₅^– salts reveal conformational differences in the anions, and the ¹⁹F NMR spectra of these salts in CH₃CN reveal coupling of the axial fluorido ligand to the ¹⁴N nucleus of the imido ligand. In addition, density functional theory (DFT-B3LYP) calculations have been performed on a series of W(NR)F₅^– anions (R = H, F, CH₃, CF₃, C₆H₅, C₆F₅) and the W₂(NC₆F₅)₂F₉^– anion, including gas-phase geometry optimizations, vibrational frequencies, molecular orbitals, and natural bond orbital (NBO) analyses.

中文翻译：

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合成和W的表征（NC ₆ ˚F ₅）的F ₅ ^-和W ₂（NC ₆ ˚F ₅）₂ ˚F ₉ ^-的W的盐和计算研究（NR）的F ₅ ^-（R = H，F，CH ₃， CF ₃，C ₆ H ₅，C ₆ F ₅）和W ₂（NC ₆ F ₅）₂ F ₉ ^–阴离子

已经开发出方便的制备方法来制备氟代[（五氟苯基）亚氨基钨酸（VI）盐]。WF ₆ ·NC ₅ H ₅或[N（CH ₃）₄ ] [WF ₇ ]与C ₆ F ₅ NH _2的反应导致定量形成C ₅ H ₅ NH ⁺或N（CH ₃）₄ ⁺在W的盐（NC ₆ ˚F ₅）的F ₅ ^-阴离子，分别。[C ₅ H ₅ NH] [W（NC ₆在无水HF中的F ₅）F ₅ ]导致形成[C ₅ H ₅ NH] [W ₂（NC ₆ F ₅）₂ F ₉ ]。这些盐已通过X射线晶体学和拉曼光谱在固态下以及在溶液中通过¹⁹ F和¹ H NMR光谱进行了全面表征。W（NC ₆ F ₅）F ₅ ^–盐的晶体结构揭示了阴离子的构象差异，这些盐在CH _3中的¹⁹ F NMR光谱CN揭示了轴向氟代配体与亚氨基配体的¹⁴ N核的偶联。此外，密度泛函理论（DFT-B3LYP）计算已在一系列W（NR）的F进行₅ ^-阴离子（R = H，F，CH ₃，CF ₃，C ₆ H ^ ₅，C ₆ ˚F ₅）和W ₂（NC ₆ ˚F ₅）₂ ˚F ₉ ^-的阴离子，其中包括气相几何优化，振动频率，分子轨道，以及自然键轨道（NBO）分析。