[bromyl][SbF6] | 58409-46-4

• 英文名称: [bromyl][SbF6]
• CAS: 58409-46-4
• 化学式: BrO₂*F₆Sb
• 分子量: 347.643
• InChiKey: OQUWNTOETQEFHD-UHFFFAOYSA-H

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：

  二氟代氙 、 [bromyl][SbF6] 在 氢氟酸 作用下， 生成
  参考文献：
  名称：

  [BrO2]+ 阳离子的 XeF2 配位化合物，[O2Br(FXeF)n][AsF6] (n = 1, 2) 和 [O2Br(FXeF)2][SbF6]；它们的合成和结构表征

  摘要：

  描述了[BrO 2 ] +阳离子的第一个 XeF 2配位络合物的合成和结构表征。[BrO 2 ][PnF 6 ] (Pn = As, Sb) 与 XeF 2在无水 HF 溶剂中的反应产生盐 [O 2 Br(FXeF) n ][AsF 6 ] ( n = 1, 2) 和 [ O 2 Br(FXeF) 2 ][SbF 6 ]，通过低温 (LT) 拉曼光谱和单晶 X 射线衍射 (SCXRD) 对其进行了表征。XeF 2配体和[PnF 6 ] -主要通过静电 Br V ---F Xe σ-空穴键与路易斯酸性 [ BrO 2 ] +阳离子配位，该键由 F 原子配位到 Br(V) 原子上的高正静电势区域并具有键合避免 Br(V) 的立体活性价电子孤对电子的轨迹。配合物及其通过 LT 拉曼光谱和 SCXRD 的结构表征显着扩展了 Br(V) 的配位化学，并提供了稀有气体二氟化物与强氧化剂主族路易斯酸中心配位的罕见例子。

  DOI：

  10.1021/acs.inorgchem.3c01030
• 作为产物：
  描述：

  bromyl fluoride 、 五氟化锑 以 氯氟磺酰 为溶剂， 生成 [bromyl][SbF6]
  参考文献：
  名称：

  二氧化溴氟化物BrO2 F用于生成价态溴氧阳离子Br3 O4 +和Br3 O6的反应。

  摘要：

  报道了不稳定和高反应性BrO2 F的可靠合成。该化合物可转化为BrO2 + SbF6--，BrO2 + AsF6-和BrO2 + AsF6--⋅2BrO2F。后者分解为五价，三价，一价，和零价溴。用HSO3 CF3形成BrO2 + H（SO3 CF3）2-。过量的BrO2 F会生成五价和三价溴的混合价Br3 O6 + OSO3 CF3。BrO2 F和MoF5在SO2 ClF或CH2 ClF中的反应生成Cl2 BrO6 + Mo3 O3 F13-。BrO2 F与（CF3 CO）2 O和NO2的反应生成O2 Br-O-CO-CF3和已知的NO2 + Br（ONO2）2-。所有这些化合物都是热力学不稳定的。

  DOI：

  10.1002/anie.201912271

文献信息

• 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.