(η⁵-C₅H₂-1,2,4-Me₃)₂ZrCl₂

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: (η⁵-C₅H₂-1,2,4-Me₃)₂ZrCl₂
• 英文别名: [(η(5)-1,2,4-trimethylcyclopentadienyl)2ZrCl2]；(Cp-1,2,4-Me3)2ZrCl2；bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride；dichlorozirconium(2+);1,3,5-trimethylcyclopenta-1,3-diene
• 化学式: C₁₆H₂₂Cl₂Zr
• 分子量: 376.481
• InChiKey: MCVPULAYJVFYAS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.33
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (η⁵-C₅H₂-1,2,4-Me₃)₂ZrCl₂ 、 碘代三甲硅烷 以 二氯甲烷 为溶剂， 反应 96.0h， 以91%的产率得到(η⁵-C₅H₃-1,2,4-Me₃)₂ZrI₂
  参考文献：
  名称：

  使用第 4 族茂金属配合物进行二氮硼化

  摘要：

  含强活化二氮配体的铪和二茂锆配合物 [(η5-C5H2-1,2,4-Me3)2M]2(μ2,η2,η2-N2) 与频哪醇硼烷 (HBPin) 硼酸化导致 N-B和 M-H 键的形成。用一氧化碳处理硼酸化产物引发 N-N 键断裂，伴随着 N-C 键的形成，产生 μ-硼酰亚氨基和 μ-甲酰氨基片段。相反，tBuNC 的添加导致异氰化物配体插入 M-H 键并提供相应的 η2-亚氨基酰基铪茂配合物。

  DOI：

  10.1002/ejic.201300046

文献信息

• 1H-, 13C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: effect of the ligand structure on the formation of active intermediates and polymerization kinetics
  作者：Konstantin P Bryliakov、Nina V Semikolenova、Dmitrii V Yudaev、Vladimir A Zakharov、Hans H Brintzinger、Martin Ystenes、Erling Rytter、Evgenii P Talsi

  DOI：10.1016/s0022-328x(03)00443-1

  日期：2003.10

  Using H-1- and C-13-NMR spectroscopies, cationic intermediates formed by activation of L2ZrCl2 with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L-2 are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)(2)ZrCl2 (R = Me, 1,2-Me2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, Me-5, n-Bu, t-Bu), rac-ethanediyl(Ind)(2)ZrCl2, rac-Me2Si(Ind)(2)ZrCl2, rac-Me2Si(1-Ind-2-Me)(2)ZrCl2, rac-ethanediyl(1-Ind-4,5,6,7-H-4)(2)ZrCl2, (Ind-2Me)(2)ZrCl2, Me2C(CP)(Flu)ZrCl2, Me2C(Cp-3-Me)(Flu)ZrCl2 and Me2Si(Flu)(2)ZrCl2- Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)(2)ZrCl2/MAO (R = H, Me, 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, Me-5, n -Bu, t-Bu) and rac-Me2Si(Ind)(2)ZrCl2 were established. The catalysts (Cp-R)(2)ZrCl2/AlMe3/CPh3+B(C6F5)(4)(-) (R= Me, 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, n -Bu, t -Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)(2)ZrMe+ <-- Me- -Al equivalent to MAO (IV) with different [Me-MAO](-) counteranions have been identified in the (Cp-R)(2)ZrCl2/MAO (R = H-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L2Zr(mu-Me)(2)AlMe2](+)[Me-MAO](-) (HI) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr = 200 - 1000) for the systems (Cp-R)(2)ZrCl2/MAO (R = H, Me, n -Bu, t -Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)(2)ZrCl2/MAO (R = 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4) and rac-Me2Si(Ind)(2)ZrCl2/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems. (C) 2003 Elsevier Science B.V. All rights reserved.