Syntheses, characterization, and computational study of WSF4 and WSF4 x CH3CN.
Syntheses, characterization, and computational study of WSF4 and WSF4 x CH3CN.
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WSF4 和 WSF4 x CH3CN 的合成、表征和计算研究。
DOI：
10.1021/ic901752w
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发表时间：
2009
影响因子：
4.6
通讯作者：
M. Gerken
中科院分区：
文献类型：
--
作者：
J. Nieboer;William Hillary;Xin Yu;H. Mercier;M. Gerken
本文提出了一种新的合成WSF（4）的改进路线，即由WF（6）和Sb（2）S（3）在无水HF中反应。采用拉曼光谱和19 F核磁共振谱首次在HF溶剂中对四氟化硫化钨进行了表征。这两项研究都为它在HF溶液中的单体形式提供了证据。在固体状态下，WSF（4）也进行了表征拉曼和红外光谱。WSF（4）与CH（3）CN在无水HF溶剂中反应，再与过量的CH（3）CN直接反应制得WSF（4）x CH（3）CN加合物，并通过固体拉曼光谱和红外光谱以及CH（3）CN溶液中的（19）F NMR光谱进行了表征。WSF（4）x CH（3）CN的晶体结构表明，CH（3）CN以端对方式与W配位，反式与W-S键配位。采用量子化学B3 LYP和PBE 1 PBE方法计算了WSF（4）和WSF（4）xCH（3）CN的气相几何构型和振动频率。
A new and improved synthetic route to WSF(4) was developed from the reaction of WF(6) and Sb(2)S(3) in anhydrous HF. Tungsten sulfide tetrafluoride was characterized by Raman and (19)F NMR spectroscopy for the first time in HF solvent. Both studies provided evidence for its monomeric form in HF solution. In the solid state, WSF(4) was also characterized by Raman and infrared spectroscopy. The WSF(4) x CH(3)CN adduct was prepared from WSF(4) and CH(3)CN in anhydrous HF solvent and by the direct combination of WSF(4) with excess CH(3)CN, and was characterized by Raman and infrared spectroscopy in the solid state and (19)F NMR spectroscopy in CH(3)CN solution. The crystal structure of WSF(4) x CH(3)CN was obtained and showed that CH(3)CN coordinates to W in an end-on fashion and trans to the W-S bond. Quantum-chemical calculations using B3LYP and PBE1PBE methods were used to calculate the gas-phase geometries and vibrational frequencies of WSF(4) and WSF(4) x CH(3)CN.