(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.
• Dinitrogen Borylation with Group 4 Metallocene Complexes
  作者：Scott P. Semproni、Paul J. Chirik

  DOI：10.1002/ejic.201300046

  日期：2013.8.6

  Borylation of hafno- and zirconocene complexes [(η5-C5H2-1,2,4-Me3)2M]2(μ2,η2,η2-N2), containing strongly activated dinitrogen ligands, with pinacolborane (HBPin) resulted in N–B and M–H bond formation. Treatment of the borylated products with carbon monoxide triggered N–N bond scission with concomitant N–C bond formation to produce μ-borylimido and μ-formamidido fragments. Conversely, addition of

  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。