(Cp*)2 difluorohafnium(IV) | 154860-98-7

• 英文名称: (Cp*)2 difluorohafnium(IV)
• 英文别名: Cp*₂HfF
• CAS: 154860-98-7
• 化学式: C₂₀H₃₀F₂Hf
• 分子量: 486.945
• InChiKey: DTXBWJHKQQTMQZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (Cp*)2 difluorohafnium(IV) 、 六氟异丙醇 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors

  摘要：

  The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)(2)], R = Et la, Cy lb, trans-[Pd(F) (4-C5NF4) (PCy3)(2)](2), trans-[Pt(F){2-C5NF2H(CF3)}-(PCy3)(2)] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability beta (Hunter scale) for the group 10 metal fluorides is far greater (la 12.1, lb 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, Sa 4.7, 6a 4.7, 4b 6.9, Sb 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to la in carbon tetrachloride (-23.5 +/- 0.3 kJ mol(-1)) interlocks our study with Laurence's scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of p pi-d pi- bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)(2)], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.

  DOI：

  10.1021/jacs.5b07509
• 作为产物：
  描述：

  (Cp*)2 dimethylhafnium(IV) 、 氟化羟基可力定 以 甲苯 为溶剂， 以82%的产率得到(Cp*)2 difluorohafnium(IV)
  参考文献：
  名称：

  2,4,6-Trimethylpyridine–bishydrofluoride: a novel fluorinating reagent for organo transition-metal alkyls

  摘要：

  Complexes [M(eta(5)-C(5)Me(5))F-3] (M = Zr 2, Hf 5), [Zr(eta(5)-C5H5)F-2] 7 and [Hf(eta(5)-C(5)Me(5))(2)F-2] 8 are obtained by treating the corresponding metal alkyls with [tmpy .(HF)(2)] (tmpy = 2,4,6-trimethylpyridine); using an excess of [tmpy .(HF)(2)] in the preparation of 2 and 5 leads to the complexes [Htmpy][{M(eta(5)-C(5)Me(5))F-2}(mu-F)(3)] (M = Zr 3, Hf 6), respectively and a crystal structure determination of 3 confirms its ionic nature; [Ti(eta(5)-C(5)Me(5))Cl2F] 10 and 2 were synthesised also from their corresponding alkyls by alkyl-fluorine exchange using Me(3)SnF.

  DOI：

  10.1039/cc9960000029

文献信息

• Activation of Aromatic, Aliphatic, and Olefinic Carbon–Fluorine Bonds Using Cp* ₂ HfH ₂
  作者：Ryan D. Rieth、William W. Brennessel、William D. Jones

  DOI：10.1002/ejic.200600802

  日期：2007.6

  The hafnium hydride Cp*2HfH2 is reacted with a series of fluorocarbons to examine the scope of C–F bond activation. Aromatic, vinylic, and aliphatic C–F bonds all show some degree of reactivity, and possible mechanisms are discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  氢化铪 Cp*2HfH2 与一系列碳氟化合物反应以检查 C-F 键活化的范围。芳香族、乙烯基和脂肪族 C-F 键都显示出一定程度的反应性，并讨论了可能的机制。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Trimethyltin Fluoride: A New Fluorinating Reagent for the Preparation of Organometallic Fluorides
  作者：Axel Herzog、Feng-Quan Liu、Herbert W. Roesky、Alojz Demsar、Klaus Keller、Mathias Noltemeyer、Frank Pauer

  DOI：10.1021/om00016a030

  日期：1994.4

  Me3SnF (1) reacts with Cp'MCl3 to give Cp'MF3 (2, Cp' = C5Me5, M = Ti; 2a, Cp' = C5Me4Et, M = Ti; 2b, Cp' = C5H5, M = Ti; 2c, Cp' = C5H4Me5, M = Ti; 3, Cp' = C5Me5, M = Zr; 4, Cp' = C5Me5, M = Hf) in high yields. The reaction of Cp2TiCl2, [C5H3(Me)(SiMe3)]2ZrCl2, and (C5Me5)2HfCl2 with Me3SnF yields Cp2TiF2 (5), [C5H3(Me) (SiMe3)]2ZrF2 (6), and (CsMe5)2HfF2 (7), respectively. Treatment of (Cp*TiClO)3 (Cp* = C5Me5) with Me3SnF leads to the eight-membered ring (Cp*TiFO)4 (8). The reaction of the organotitanium(III) chlorides (Cp2TiCl)2 (Cp = C5H5), [(C5H4Me)2TiCl]2, and Cp*2TiCl with Me3SnF gives the corresponding fluorides (Cp2TiF)2 (9), [(C5H4Me)2TiF]2 (10), and Cp2*TiF (11), respectively. An alternative method for the preparation of compounds 9 and 10 is the reduction of Cp2TiF2 and (C5H4Me)2TiF2, respectively, using sodium amalgam. The structures of 2c, 3, 4, and 10 were determined by single-crystal X-ray diffraction. Compounds 3 and 4 are isostructural and form tetramers in the solid as well as in solution. 10 is a fluorine-bridged dimer in the crystalline state.