tetrafluoro-bis(triphenylphosphine oxide)hafnium(IV) | 1404564-06-2

• 英文名称: tetrafluoro-bis(triphenylphosphine oxide)hafnium(IV)
• 英文别名: [HfF4(OPPh3)2]
• CAS: 1404564-06-2
• 化学式: C₃₆H₃₀F₄HfO₂P₂
• 分子量: 811.064
• InChiKey: COMYDSOPHRGIQN-UHFFFAOYSA-J

计算性质

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

• 作为产物：
  描述：

  cis-tetrafluoro-bis(N,N-dimethylformamide)-hafnium(IV) 、 三苯基氧化膦 以 N,N-二甲基甲酰胺 、 二氯甲烷 为溶剂， 反应 5.0h， 以55%的产率得到tetrafluoro-bis(triphenylphosphine oxide)hafnium(IV)
  参考文献：
  名称：

  极硬路易斯酸ZrF 4和HfF 4 †的配位化合物的制备和结构

  摘要：

  通过将MF 4 · n H 2 O溶解在适当的溶剂中制备的[MF 4（dmso）2 ]（M = Zr或Hf）和[MF 4（dmf）2 ]被用作各种配合物的合成子。这些难于处理的四氟化物中的一种。这些试剂在无水CH 2 Cl 2中与OPR 3（R = Me或Ph）或OAsPh 3（L）反应形成六配位[MF 4 L 2 ]，它们以顺式（主要形式）和反式异构体的混合物形式存在在CH 2 Cl 2中溶液，但结晶为反式（OPPh 3，OAsPh 3）或顺式（OPMe 3）形式。顺式- [ZRF 4（OAsPh 3）2 ]从MeCN中得到的晶体。顺式-[MF 4（pyNO）2 ]和八坐标（扭曲的十二面体）[MF 4（L–L）2 ]（L = 2，2'-bipy或1,10-phen），和[ MF 4（我4-cyclam）]。尝试与N-杂环卡宾，1,3-（2,6-二异丙基苯基）咪唑-2-亚烷基（IDiPP）

  DOI：

  10.1039/c2dt31501g

文献信息

• Synthesis and equilibria in solutions of hafnium fluoro complexes with phosphoryl-containing bases Ph3PO, Bu3PO, and (Me2N)3PO
  作者：V. V. Kovalev、E. G. Il’in

  DOI：10.1134/s0036023616090114

  日期：2016.9

  The composition and equilibria in solutions of the products of reaction of HfF4(dmso)(2) with monodentate phosphoryl-containing bases L = Ph3PO, Bu3PO, and (Me2N)(3)PO in CH2Cl2 are studied by F-19 NMR. Octahedral molecular complexes cis-[HfF4L2] and minor amounts of trans-[HfF4L2] and fac[HfF3L3](+) cations were the main products for all ligands. The oxytrifluoride complex (mu-O)[HfF3(Bu3PO)(2)](2) and the [HfF5(Bu3PO)](-) anion were identified in the case of Bu3PO. The conclusion about the formation of the hafnium oxytrifluoro complex was verified via hydrolysis of the product of reaction between HfF4 and Ph3PO upon exposure to air. As a result, (mu-O)[HfF3(Ph3PO)(2)](2) were detected; fine-structure F-19 NMR resonance lines were obtained and the spin-spin coupling constant JFF was measured for the first time. Hydrolysis via adding a Bu4NOH solution in i-PrOH to the HfF4L2 solutions in CH2Cl2 did not yield the expected zirconium oxyfluoro complexes with the smaller number of fluorine atoms. Due to deeper hydrolysis, equilibrium in fluoride complexes shifted towards species with higher fluorine contents, [ZrF5L](-) and [ZrF6](2-), resulting in the formation of Hf(O)(x)(OH)(y)(i-PrOH)(z) complexes that were not observed in the F-19 NMR spectra and the substitution of the released fluoride ions for molecular ligands in HfF4L2 complexes.