bis[η5-(2-phenylindenyl)]zirconium dichloride | 163167-60-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis[η5-(2-phenylindenyl)]zirconium dichloride
• 英文别名: bis(2-phenylindenyl)zirconium dichloride；(2-Phenylindene)₂ZrCl₂；(2-PhInd)₂ZrCl₂；[(2-PhInd)2ZrCl2]；2-phenyl-1H-inden-1-ide;zirconium(4+);dichloride
• CAS: 163167-60-0
• 化学式: C₃₀H₂₂Cl₂Zr
• 分子量: 544.635
• InChiKey: NHXJKCSKQSEIJR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.83
• 重原子数：
  33
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis[η5-(2-phenylindenyl)]zirconium dichloride 在 methylaluminoxane 作用下， 以 氘代甲苯 为溶剂， 生成 [(2-PhInd)2ZrClMe]
  参考文献：
  名称：

  ¹H and ¹³C NMR Studies of Cationic Intermediates Formed upon Activation of “Oscillating” Catalyst (2-PhInd)₂ZrCl₂ with MAO, MMAO, and AlMe₃/[CPh₃]⁺[B(C₆F₅)₄]^-

  摘要：

  The conformationally dynamic unbridged metallocene (2-PhInd)(2)ZrCl2 (1-Cl) was activated with methylaluminoxane (MAO), modified methylaluminoxane (MMAO), and AlMe3/[CPh3](+)[B(C6F5)(4)](-). The following ion pairs were characterized by H-1 and C-13 NMR: [(2-PhInd)(2)Zr(mu-Me)(2)AlMe2](+)[Me-MAO](-) (III), [(2-PhInd)(2)Zr(mu-Me)(2)AlMe2](+)[B(C6F5)(4)](-) (III'), [(2-PhInd)(2)Zr(mu-Me)(2)(AlMeBu)-Bu-i](+)[Me-MAO](-) (IIIMeiBu), [(2-PhInd)(2)Zr(mu-Me)(2)(AlBu2)-Bu-i](+)[Me-MAO](-) (IIiBuiBu), and [(2-PhInd)(2)ZrMe+center dot center dot center dot Me-MAO(-)] (IV). In the temperature range -50 to 20 degrees C, the rotation of indenyl ligands of complexes III, II', and III/(MeiBu) is faster than the evaluated rate of propylene insertion, whereas for IIIiBuiBu the rate of indenyl ligand rotation is comparable to or slower than the rate of propylene insertion. The ion pair BOIIIBOiBuiBu demonstrates the fundamental possibility of the existence of intermediates with the "locked" conformation of 2-PhInd ligands in 1-Cl/MAO or 1-Cl/MMAO systems. For the catalytic system 1-Cl/MAO, both outer sphere ion pair III and inner sphere ion pair IV are present in the reaction solution at high [Al](MAO)/[Zr] ratios. For the catalytic system 1-Cl/MAO, the concentration of inner sphere ion pairs of type IV is much smaller (below the NMR detection limit), and only outer sphere ion pairs IIMeiBu and IIIiBuiBu are observed.

  DOI：

  10.1021/om0610694
• 作为产物：
  描述：

  2-苯基茚 、 氯化锆(IV) 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 bis[η5-(2-phenylindenyl)]zirconium dichloride
  参考文献：
  名称：

  具有单取代茚基配体的未桥接茂金属二氯化物络合物及其在丙烯聚合中的应用

  摘要：

  该型IND'的桥连的茂金属二氯化物络合物的合成2的ZrCl 2（茚'= 2 -烷基-或芳基-取代的茚基）进行说明。该复合物的特征在于1 H-和13 C-NMR光谱法和质谱法。用甲基铝氧烷活化后，这些络合物可用于丙烯聚合。他们生产的嵌段共聚物由交替的等规和无规嵌段组成。给出了聚合结果和聚合物性能。讨论了催化剂结构对聚合行为的影响。

  DOI：

  10.1016/s0022-328x(00)00776-2

文献信息

• Propylene Polymerization with Unbridged Metallocenes:  Ligand Effects on the Selectivity for Elastomeric Polypropylene
  作者：Jennifer L. Maciejewski Petoff、Michael D. Bruce、Robert M. Waymouth、Athar Masood、Tapan K. Lal、Roger W. Quan、Steven J. Behrend

  DOI：10.1021/om9706119

  日期：1997.12.1

  elastomeric polypropylene with a stereoblock microstructure. In an effort to experimentally explore the importance of the 2-arylindene ligand in producing these materials, a series of catalysts was investigated that differed significantly from the parent ligand architecture. In particular, we sought to examine the influence of ligand aryl stacking on the polymerization behavior of these metallocenes. We discovered

  由甲基铝氧烷活化的双（2-芳基茚基）二氯化锆可生产具有立体嵌段微结构的弹性聚丙烯。为了通过实验探索2-芳基茚配体在生产这些材料中的重要性，研究了一系列与母体配体结构显着不同的催化剂。特别地，我们试图检验配体芳基堆积对这些茂金属的聚合行为的影响。我们发现，双（2-芳基茚基）骨架对于通过这种类型的未桥连配合物生产弹性聚丙烯是重要的。基本催化剂结构的微小变化破坏了配体旋转和单体插入之间的微妙平衡，从而导致了无定形聚合物的产生。
• Strategies for Synthesis of Elastomeric Polypropylene: Fluxional Metallocenes with <i>C</i>₁-Symmetry
  作者：Raisa Kravchenko、Athar Masood、Robert M. Waymouth、Charles L. Myers

  DOI：10.1021/ja973414+

  日期：1998.3.1

  2-phenylindenyl-type ligands in bis(2-phenylindenyl)zirconium dichloride, (2-PhInd)2ZrCl2 (7), a catalyst precursor for the production of elastomeric polypropylene (ELPP-7), with a cyclopentadienyl-type ligand have been studied. The mixed-ring compounds: (pentamethylcyclopentadienyl)(2-phenylindenyl)zirconium dichloride, Cp*(2-PhInd)ZrCl2, (8), (pentamethylcyclopentadienyl)(1-methyl-2-phenylindenyl)zirconium

  用双(2-苯基茚基)二氯化锆 (2-PhInd)2ZrCl2 (7)（一种用于生产弹性聚丙烯 (ELPP-7) 的催化剂前体）替换 2-苯基茚基型配体之一的效果已经研究了环戊二烯基型配体。混环化合物：（五甲基环戊二烯基）（2-苯基茚基）二氯化锆，Cp*（2-PhInd）ZrCl2，（8），（五甲基环戊二烯基）（1-甲基-2-苯基茚基）二氯化锆，Cp*（1- Me-2-PhInd)ZrCl2 (9) 和（环戊二烯基）（2-苯基茚基）二氯化锆，Cp(2-PhInd)ZrCl2 (10)，已经通过相应的茚化锂与 C5R5ZrCl3（8 和9：R = CH3；10：R = H）。已确定配合物 8 和 9 的晶体结构。 衍生自配合物 8、9、和 10 在它们被甲基铝氧烷 (MAO) 活化后用于乙烯和丙烯聚合的研究。在所有混合环催化剂中，只有 8/MAO 生产弹性聚丙烯 (ELPP-...
• Unbridged metallocene dichloride complexes with mono-substituted indenyl ligands and their application for the polymerization of propene
  作者：Roland Schmidt、Helmut G Alt

  DOI：10.1016/s0022-328x(00)00776-2

  日期：2001.3

  synthesis of unbridged metallocene dichloride complexes of the type Ind′2ZrCl2 (Ind′=2-alkyl- or arylalkyl-substituted indenyl) is described. The complexes are characterized by 1H- and 13C-NMR spectroscopy and mass spectrometry. After activation with methylalumoxane these complexes can be used for propene polymerization; they produce block copolymers consisting of alternating isotactic and atactic blocks

  该型IND'的桥连的茂金属二氯化物络合物的合成2的ZrCl 2（茚'= 2 -烷基-或芳基-取代的茚基）进行说明。该复合物的特征在于1 H-和13 C-NMR光谱法和质谱法。用甲基铝氧烷活化后，这些络合物可用于丙烯聚合。他们生产的嵌段共聚物由交替的等规和无规嵌段组成。给出了聚合结果和聚合物性能。讨论了催化剂结构对聚合行为的影响。
• Effect of Metal on the Stereospecificity of 2-Arylindene Catalysts for Elastomeric Polypropylene
  作者：Michael D. Bruce、Geoffrey W. Coates、Elisabeth Hauptman、Robert M. Waymouth、Joseph W. Ziller

  DOI：10.1021/ja971895r

  日期：1997.11.1

  hafnium-based catalysts yield polypropylenes that are significantly less isotactic than the corresponding zirconium compounds, although molecular weights and productivities were similar for hafnium and zirconium derivatives. The X-ray crystal studies of these catalysts show nearly identical structures for corresponding zirconium and hafnium compounds. Variable temperature NMR of the metallocene dibenzyl

  丙烯与双(2-苯基茚基)二氯化锆和双(2-[3,5-双三氟甲基)茚基]二氯化锆聚合生成弹性聚丙烯。这些聚合物的弹性性能已被解释为立体嵌段微结构。通过 13 C NMR 对微观结构的分析表明，全同立构五单元组含量 [mmmm] 范围为 6% 至 74%。研究铪衍生物以探究过渡金属对聚合行为的影响。尽管铪和锆衍生物的分子量和生产率相似，但铪基催化剂产生的聚丙烯的全同立构规整度明显低于相应的锆化合物。这些催化剂的 X 射线晶体研究表明，相应的锆和铪化合物具有几乎相同的结构。茂金属二苄基类似物的变温 NMR 表现出与茚基配体的旋转一致的行为，其中茚基的旋转...
• ¹H and ¹³C NMR Studies of Cationic Intermediates Formed upon Activation of “Oscillating” Catalyst (2-PhInd)₂ZrCl₂ with MAO, MMAO, and AlMe₃/[CPh₃]⁺[B(C₆F₅)₄]^-
  作者：Oleg Y. Lyakin、Konstantin P. Bryliakov、Nina V. Semikolenova、Artem Y. Lebedev、Alexander Z. Voskoboynikov、Vladimir A. Zakharov、Evgenii P. Talsi

  DOI：10.1021/om0610694

  日期：2007.3.1

  The conformationally dynamic unbridged metallocene (2-PhInd)(2)ZrCl2 (1-Cl) was activated with methylaluminoxane (MAO), modified methylaluminoxane (MMAO), and AlMe3/[CPh3](+)[B(C6F5)(4)](-). The following ion pairs were characterized by H-1 and C-13 NMR: [(2-PhInd)(2)Zr(mu-Me)(2)AlMe2](+)[Me-MAO](-) (III), [(2-PhInd)(2)Zr(mu-Me)(2)AlMe2](+)[B(C6F5)(4)](-) (III'), [(2-PhInd)(2)Zr(mu-Me)(2)(AlMeBu)-Bu-i](+)[Me-MAO](-) (IIIMeiBu), [(2-PhInd)(2)Zr(mu-Me)(2)(AlBu2)-Bu-i](+)[Me-MAO](-) (IIiBuiBu), and [(2-PhInd)(2)ZrMe+center dot center dot center dot Me-MAO(-)] (IV). In the temperature range -50 to 20 degrees C, the rotation of indenyl ligands of complexes III, II', and III/(MeiBu) is faster than the evaluated rate of propylene insertion, whereas for IIIiBuiBu the rate of indenyl ligand rotation is comparable to or slower than the rate of propylene insertion. The ion pair BOIIIBOiBuiBu demonstrates the fundamental possibility of the existence of intermediates with the "locked" conformation of 2-PhInd ligands in 1-Cl/MAO or 1-Cl/MMAO systems. For the catalytic system 1-Cl/MAO, both outer sphere ion pair III and inner sphere ion pair IV are present in the reaction solution at high [Al](MAO)/[Zr] ratios. For the catalytic system 1-Cl/MAO, the concentration of inner sphere ion pairs of type IV is much smaller (below the NMR detection limit), and only outer sphere ion pairs IIMeiBu and IIIiBuiBu are observed.