perbromyl fluoride | 25251-03-0

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 卤代有机物
• 英文名称: perbromyl fluoride
• CAS: 25251-03-0
• 化学式: BrFO₃
• 分子量: 146.901
• InChiKey: FHRGMUIQMATFDZ-UHFFFAOYSA-N

物化性质

• 沸点：
  2.38°C (estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  perbromyl fluoride 、 五氟化锑 以 melt 为溶剂， 生成 [bromyl][SbF6]
  参考文献：
  名称：

  Behavior of BrO₃F and ClO₃F Toward Strong Lewis Acids and the Characterization of [XO₂][SbF₆] (X = Cl, Br) by Single Crystal X-ray Diffraction, Raman Spectroscopy, and Computational Methods

  摘要：

  The interactions of BrO3F and ClO3F with the strong Lewis acids AsF5 and SbF5 were investigated. Although ClO3F is unreactive toward AsF5 and SbF5, BrO3F undergoes fluoride ion abstraction and O-2 elimination, accompanied by central halogen reduction, to form [BrO2][SbnF5n+1] (n >= 1), rather than simple fluoride ion abstraction to form BrO3+ salts. The geometric parameters of the BrO2+ cation have been obtained in the solid state for the first time by a single-crystal X-ray diffraction study of [BrO2][SbF6] at -173 degrees C and are compared with those of ClO2+ salts. Quantum-chemical calculations have been used to arrive at the geometries and vibrational frequencies of XO2+ and XO3+ (X = Cl, Br) and have been compared with the experimental values for XO2+. The calculations have also been used to account for the contrasting behaviors Of ClO3F and BrO3F toward central halogen reduction in the presence of liquid SbF5. The thermochemical stabilities of ClO3+ and BrO3+ salts of the AsF6-, SbF6-, Sb2F(11)(-), and Sb3F16- were also investigated, which provided the fluoride ion affinities of AsF5, SbF5, Sb2F10, and Sb3F15 up to and including the CCSD(T) level of theory. These values are compared with the current literature values. Thermochemical studies indicate that XO3+ formation by fluoride ion abstraction from XO3F is not spontaneous under standard conditions whereas a concerted fluoride abstraction and O-2 elimination to give the XO2+ cations is spontaneous to near thermally neutral. Failure to observe reactivity between ClO3F and any of the aforementioned Lewis acid fluoride ion acceptors is attributed to a significant kinetic barrier to fluoride ion abstraction.

  DOI：

  10.1021/ic800929h
• 作为产物：
  描述：

  过溴酸钾 、 氢氟酸 、 五氟化砷 以 氢氟酸 为溶剂， 生成 perbromyl fluoride
  参考文献：
  名称：

  含 BrO3F2-阴离子盐的合成和表征；溴 (VII) 物种的罕见例子

  摘要：

  BrO(3)F(2)(-) 阴离子是通过 BrO(3)F 与氟离子供体 KF、RbF、CsF、[N(CH(3))(4)][F] 反应制备的，和 NOF。BrO(3)F(2)(-) 阴离子是第四个以宏观数量分离的 Br(VII) 物种，它是仅有的三种具有 D(3)(h)() 的氧化物氟化物之一对称性，其他是 XeO(3)F(2) 和 OsO(3)F(2)。BrO(3)F 的氟离子受体特性与 ClO(3)F 的特性形成对比，ClO(3)F 不与强氟离子供体 [N(CH(3))(4)][F] 反应形成类似的ClO(3)F(2)(-) 盐。[NO](2)[BrO(3)F(2)][F]和[N(CH(3))(4)][BrO(3)F(2)]的单晶X射线结构] 确认 BrO(3)F(2)(-) 阴离子的 D(3)(h)() 对称性并提供准确的 Br-O (1.593(3)-1.610(6) A) 和 Br-F

  DOI：

  10.1021/ja0402607

文献信息

• Synthesis and Characterization of Salts Containing the BrO₃F₂^- Anion; A Rare Example of a Bromine(VII) Species
  作者：John F. Lehmann、Gary J. Schrobilgen

  DOI：10.1021/ja0402607

  日期：2005.7.1

  02(7) A(3), Z = 2, and R(1) = 0.0314 at -173 degrees C. The (19)F chemical shift of [N(CH(3))(4))][BrO(3)F(2)] in CH(3)CN is 237.0 ppm and is more deshielded than those of the previously investigated Br(VII) species, BrO(3)F and BrF(6)(+). The vibrational frequencies of the BrO(3)F(2)(-) anion were determined by use of Raman and infrared spectroscopy and were assigned with the aid of electronic structure

  BrO(3)F(2)(-) 阴离子是通过 BrO(3)F 与氟离子供体 KF、RbF、CsF、[N(CH(3))(4)][F] 反应制备的，和 NOF。BrO(3)F(2)(-) 阴离子是第四个以宏观数量分离的 Br(VII) 物种，它是仅有的三种具有 D(3)(h)() 的氧化物氟化物之一对称性，其他是 XeO(3)F(2) 和 OsO(3)F(2)。BrO(3)F 的氟离子受体特性与 ClO(3)F 的特性形成对比，ClO(3)F 不与强氟离子供体 [N(CH(3))(4)][F] 反应形成类似的ClO(3)F(2)(-) 盐。[NO](2)[BrO(3)F(2)][F]和[N(CH(3))(4)][BrO(3)F(2)]的单晶X射线结构] 确认 BrO(3)F(2)(-) 阴离子的 D(3)(h)() 对称性并提供准确的 Br-O (1.593(3)-1.610(6) A) 和 Br-F
• Behavior of BrO₃F and ClO₃F Toward Strong Lewis Acids and the Characterization of [XO₂][SbF₆] (X = Cl, Br) by Single Crystal X-ray Diffraction, Raman Spectroscopy, and Computational Methods
  作者：John F. Lehmann、Sebastian Riedel、Gary J. Schrobilgen

  DOI：10.1021/ic800929h

  日期：2008.9.15

  The interactions of BrO3F and ClO3F with the strong Lewis acids AsF5 and SbF5 were investigated. Although ClO3F is unreactive toward AsF5 and SbF5, BrO3F undergoes fluoride ion abstraction and O-2 elimination, accompanied by central halogen reduction, to form [BrO2][SbnF5n+1] (n >= 1), rather than simple fluoride ion abstraction to form BrO3+ salts. The geometric parameters of the BrO2+ cation have been obtained in the solid state for the first time by a single-crystal X-ray diffraction study of [BrO2][SbF6] at -173 degrees C and are compared with those of ClO2+ salts. Quantum-chemical calculations have been used to arrive at the geometries and vibrational frequencies of XO2+ and XO3+ (X = Cl, Br) and have been compared with the experimental values for XO2+. The calculations have also been used to account for the contrasting behaviors Of ClO3F and BrO3F toward central halogen reduction in the presence of liquid SbF5. The thermochemical stabilities of ClO3+ and BrO3+ salts of the AsF6-, SbF6-, Sb2F(11)(-), and Sb3F16- were also investigated, which provided the fluoride ion affinities of AsF5, SbF5, Sb2F10, and Sb3F15 up to and including the CCSD(T) level of theory. These values are compared with the current literature values. Thermochemical studies indicate that XO3+ formation by fluoride ion abstraction from XO3F is not spontaneous under standard conditions whereas a concerted fluoride abstraction and O-2 elimination to give the XO2+ cations is spontaneous to near thermally neutral. Failure to observe reactivity between ClO3F and any of the aforementioned Lewis acid fluoride ion acceptors is attributed to a significant kinetic barrier to fluoride ion abstraction.