(η(2)-formaldehyde)zirconocene dimer | 83385-20-0

• 英文名称: (η(2)-formaldehyde)zirconocene dimer
• 英文别名: (η2-formaldehyde)zirconocene
• CAS: 83385-20-0
• 化学式: C₂₂H₂₄O₂Zr₂
• 分子量: 502.879
• InChiKey: XYYCLLHRDRGQSL-UHFFFAOYSA-N

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

• 作为反应物：
  描述：

  (η(2)-formaldehyde)zirconocene dimer 、 三苯基氯硅烷 以 四氢呋喃 为溶剂， 以67%的产率得到((triphenylsiloxy)methyl)zirconocene chloride
  参考文献：
  名称：

  （甲硅烷氧基甲基）锆茂金属配合物的形成和重排

  摘要：

  The zirconocene eta2-formaldehyde dimer 6 reacts with trialkylchlorosilanes R3SiCl (R = ethyl, methyl, isopropyl) to yield the (eta2-(trialkylsiloxy)methyl)zirconocene chloride complexes Cp2-Zr(Cl)CH2OSiR, (7a-c). These complexes exhibit internal O-coordination; they belong to a metallaoxirane structural type. Thermolysis of 7b,c at 110-degrees-C leads to equilibration with the isomers 8b,c and 9b,c. Complexes 8 are the acyclic CP2Zr(Cl)CH2OSiR3 isomers of 7, whereas dyotropic rearrangement has resulted in the formation of the CP2Zr(Cl)OCH2SiR3 products 9. The kinetics of the thermally induced rearrangement of 7b (R = CH3) is described by a 8b half arrow right over half arrow left 7b --> 9b kinetic scheme. At 110-degrees-C the K(8b half arrow right over half arrow left 7b) equilibrium constant is 0.35. The Gibbs activation energy of the 7b --> 8b isomerization at 110-degrees-C is DELTAG(double dagger)isom(383 K) = 30.9 +/- 0.5 kcal mol-1. The activation barrier of the 7b --> 9b transformation is in the expected range of a concerted dyotropic rearrangement process at DELTAG(double dagger)dyo(383 K) = 31.5 +/- 0.5 kcal mol-1. Treatment of 6 with triphenylchlorosilane has resulted in the direct formation of the acyclic addition product CP2Zr(Cl)CH2OSiPh3 (8d). Our study underlines the important participation of metallaoxirane type structures in dyotropic rearrangement systems.

  DOI：

  10.1021/om00014a018
• 作为产物：
  描述：

  bis(cyclopentadienyl)dihydrozirconium 在 一氧化碳 作用下， 以 甲苯 为溶剂， 以13%的产率得到(η(2)-formaldehyde)zirconocene dimer
  参考文献：
  名称：

  Erker, Gerhard; Kropp, Kurt; Krueger, Carl, Chemische Berichte, 1982, vol. 115, # 7, p. 2447 - 2460

  摘要：

  DOI：

文献信息

• A heterobimetallic Zr,Hf(μ-formaldehyde) complex from [(CH2O)ZrCp2]-dimer and hafnocene dichloride
  作者：Gerhard Erker、Miguel Mena、Maximilian Bendix

  DOI：10.1016/0022-328x(91)83032-y

  日期：1991.6

  The reaction of (η2-formaldehyde)zirconocene dimer (3) with hafnocene dichloride (5) at room temperature gives the heterobimetallic complex [μ-(η1-O: η2-C,O-formaldehyde)(Cp2ZrCl)(Cp2HfCl)]. From thermochemical considerations it is suggested that methylene migration from zirconium to hafnium occurs during the reaction, favouring the regioisomer Cp2(Cl)Zr-f(Cl)Cp2 (7) under equilibrium conditions.

  （η的反应2 -甲醛）锆茂二聚体（3）与二氯化茂铪（5）在室温下给出的异络合物[μ-（η 1 -O：η 2 -C，O-甲醛）（CP 2的ZrCl） （CP 2 HfCl）]。从热化学考虑，建议在反应过程中发生亚甲基从锆迁移到ha的现象，这在平衡条件下有利于区域异构体CP 2（Cl）Zr- f（Cl）CP 2（7）。
• Borane Insertion into Group-4 Metal-to-Carbon Bonds: The Reaction of HB(C6F5)2 with (η2-Formaldehyde)zirconocene Dimer and with (Butadiene)zirconocene
  作者：Ulrich Blaschke、Gerhard Erker、Roland Fröhlich、Oliver Meyer

  DOI：10.1002/(sici)1099-0682(199912)1999:12<2243::aid-ejic2243>3.0.co;2-0

  日期：1999.12

  (η2-Formaldehyde)zirconocene dimer (8) cleanly adds one or two molar equivalents of the borane HB(C6F5)2 by insertion of the H–[B] unit into the zirconium–carbon bond of the metallaoxirane moieties to form the mono- and bis-insertion products 16 and 17, respectively. These systems contain five-membered heterocyclic rings that are built up by connecting five different elements, namely H, B, C, O, and

  (η2-甲醛) 锆茂二聚体 (8) 通过将 H-[B] 单元插入金属环氧乙烷部分的锆 - 碳键中，干净地添加一或两摩尔当量的硼烷 HB(C6F5)2，形成单-和双插入产物分别为 16 和 17。这些系统包含五元杂环，这些环是通过连接五个不同的元素（即 H、B、C、O 和 Zr）构成的。双(硼烷)插入产物17通过X射线晶体结构分析表征。（丁二烯）锆茂以类似的方式与 HB（ ）2 反应，将 H-[B] 单元插入（丁二烯）C4-Zr 键中，形成金属环 18。