[XeF(thiazyl trifluoride)][AsF6] | 929195-60-8

• 英文名称: [XeF(thiazyl trifluoride)][AsF6]
• CAS: 929195-60-8
• 化学式: AsF₆*F₄NSXe
• 分子量: 442.268
• InChiKey: HQJLRTZEEJNFQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [XeF(thiazyl trifluoride)][AsF6] 以 neat (no solvent, solid phase) 为溶剂， 生成 、 氢氟酸
  参考文献：
  名称：

  Smith, Gregory L.; Mercier, Helene P. A.; Schrobilgen, Gary J., Journal of the American Chemical Society, 2009, vol. 131, p. 7272 - 7286

  摘要：

  DOI：
• 作为产物：
  描述：

  thiazyl trifluoride 、 xenon difluoride * AsF5 以 neat (no solvent) 为溶剂， 生成 [XeF(thiazyl trifluoride)][AsF6]
  参考文献：
  名称：

  [F3S（三键）NXeF] [AsF6]的合成和通过多核磁共振和拉曼光谱，电子结构计算和X射线晶体学的结构研究。

  摘要：

  盐[F3S（三键）NXeF] [AsF6]是通过[XeF] [AsF6]与液态N（三键）SF3在-20℃下反应合成的。Xe-N键合的阳离子提供了氙与无机氮基键合的稀有例子，其中氮被正式sp-杂化。F3S（三键）NXeF +阳离子的特征是，在-150℃下进行拉曼光谱分析，并在-20°C的HF溶液中和在-60°C的BrF5溶液中进行129Xe，19F和14N NMR光谱分析。无色[F3S（在-45℃下从HF溶剂中结晶出三键）NXeF] [AsF6]，并测定了其低温X射线晶体结构。Xe-N键是已知最长的Xe-N键（2.236（4）A）之一，而Xe-F键长度（1.938（3）A）明显短于XeF2，但长于XeF +盐。Xe-F和Xe-N键的长度与HC（三键）NXeF +的长度相似，这使其成为已知离子性最高的Xe-N键之一。非线性Xe-NS角（142.6（3）o）与通过电子结构计算预测的线性角形成对比，并归因于晶体晶胞内N

  DOI：

  10.1021/ic061899+

文献信息

• F₅SN(H)Xe⁺; a Rare Example of Xenon Bonded to sp³-Hybridized Nitrogen; Synthesis and Structural Characterization of [F₅SN(H)Xe][AsF₆]
  作者：Gregory L. Smith、Hélène P. A. Mercier、Gary J. Schrobilgen

  DOI：10.1021/ic702039f

  日期：2008.5.19

  The salt [F5SN(H)Xe][AsF6] has been synthesized by the reaction of [F5SNH3][AsF6] with XeF2 in anhydrous HF (aHF) and BrF5 solvents and by solvolysis of [F3S equivalent to NXeF][AsF6] in aHF. Both F5SN(H)Xe+ and F5SNH3+ have been characterized by Xe-129, F-19, and H-1 NMR spectroscopy in aHF (-20 degrees C) and BrF5 (supercooled to -70 degrees C). The yellow [F5SN(H)Xe][AsF6] salt was crystallized from aHF at -20 degrees C and characterized by Raman spectroscopy at -45 degrees C and by single-crystal X-ray diffraction at -173 degrees C. The Xe-N bond length. (2,069(4) angstrom) of the F5SN(H)Xe+ cation is among the shortest Xe-N bonds presently known. The cation interacts with the AsF6- anion by means of a Xe --- F-As bridge in which the Xe --- F distance (2.634(3) angstrom) is significantly. less than the sum of the Xe and F van der Waals radii (3.63 angstrom) and the AsF6- anion is significantly distorted from Oh symmetry. The F-19 and Xe-129 NMR spectra established that the [F5SN(H)Xe][AsF6] ion pair is dissociated in aHF and BrF5 solvents. The F5SN(H)Xe+ cation decomposes by HF solvolysis to F5SNH3+ and XeF2, followed by solvolysis of F5SNH3+ to SF6 and NH4+center dot angstrom minor decomposition channel leads to small quantities of F5SNF2. The colorless salt, [F5SNH3][AsF6], was synthesized by the HF solvolysis of F3S equivalent to NAsF5 and was crystallized from aHF at -35 degrees C. The salt was characterized by Raman spectroscopy at -160 degrees C, and its unit cell parameters were determined by low-temperature X-ray diffraction. Electronic structure calculations using MP2 and DFT methods were used to calculate the gas-phase geometries, charges, bond orders, and valencies as well as the vibrational frequencies of F5SNH3+ and F5SN(H)Xe+ and to aid in the assignment of their experimental vibrational frequencies. In addition to F5TeN(H)Xe+, the F5SN(H)Xe+ cation provides the only other example of xenon bonded to an Sp(3)-hybridized nitrogen center that has been synthesized and structurally characterized. These cations represent the strongest Xe-N bonds that are presently known.