difluorochloronium hexafluoroarsenate(V) | 19154-21-3

• 英文名称: difluorochloronium hexafluoroarsenate(V)
• CAS: 19154-21-3
• 化学式: AsF₆*ClF₂
• 分子量: 262.362
• InChiKey: MSEXGVIRLTXDOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.98
• 重原子数：
  10.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  、 一氟化氯 以 氢氟酸 为溶剂， 生成 difluorochloronium hexafluoroarsenate(V)
  参考文献：
  名称：

  The N2F+ cation. An unusual ion containing the shortest presently known nitrogen-fluorine bond

  摘要：

  The N2F+AsF6- salt was prepared in high yield from trans-N2F2 by thermal trans-cis isomerization in the presence of AsF5 at 70-degrees-C. A displacement reaction between N2F+AsF6- and FNO yields exclusively cis-N2F2. The Lewis acids BF3 and PF5 do not form a stable adduct with cis-N2F2 at temperatures as low as -78-degrees-C and do not catalyze the N2F2 trans-cis isomerization. A semiempirical molecular orbital model is used to explain the puzzling differences in the reaction chemistry of cis- and trans-N2F2. The crystal structure of N2F+AsF6- (monoclinic, C2/m, a = 9.184 (5) angstrom, b = 5.882 (2) angstrom, c = 5.160 (2) angstrom, beta = 90.47 (4)-degrees, Z = 2) was determined. Alternate space groups (Cm and C2) can be rejected on the basis of the observed vibrational spectra. Since in C2/m the N2F+ cations are disordered, only the sum of the N-F and N-N bond distances could be determined from the X-ray data. Local density functional calculations were carried out for N2F+ and the well-known isoelectronic FCN molecule. The results from these calculations allowed the sum of the N2F+ bond lengths to be partitioned into the individual bond distances. The resulting N-F bond length of 1.217 angstrom is by far the shortest presently known N-F bond, while the N-N bond length of 1.099 angstrom is comparable to the shortest presently known N-N bond length of 1.0976 (2) angstrom in N2. The surprising shortness of both bonds is attributed to the high s-character (sp hybrid) of the sigma-bond orbitals on nitrogen and the formal positive charge on the cation. Thus, the shortening of the N-F bond on going from sp3-hybridized NF4+ (1.30 angstrom) to sp-hybridized N2F+ (1.22 angstrom) parallels those found for the C-H and C-F bonds in the CH4, CH2 = CH2, CH = CH and CF4, CF2 = CF2, FC = N series, respectively. The oxidative power of N2F+ has also been studied. The N2F+ cation oxidized Xe and ClF to XeF+ and ClF2+, respectively, but did not oxidize ClF5, BrF5, IF5, XeF4, NF3, or O2.

  DOI：

  10.1021/ja00010a023

文献信息

• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cl: SVol.B2, 118, page 568 - 570
  作者：

  DOI：——

  日期：——
• Seel, F.; Detmer, O., Zeitschrift fur Anorganische und Allgemeine Chemie
  作者：Seel, F.、Detmer, O.

  DOI：——

  日期：——
• Seel, F.; Detmer, O., Angewandte Chemie, 1958, vol. 70, p. 163 - 164
  作者：Seel, F.、Detmer, O.

  DOI：——

  日期：——