(S,S)-ethylene(Ind)2ZrMe2 | 956483-58-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: (S,S)-ethylene(Ind)2ZrMe2
• 英文别名: rac-[(C2H4(1-indenyl)2)ZrMe2]；carbanide;1-(2-inden-1-id-1-ylethyl)inden-1-ide;zirconium(4+)
• CAS: 956483-58-2
• 化学式: C₂₂H₂₂Zr
• 分子量: 377.641
• InChiKey: KQHWXXPKUYEZIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.11
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.09
• 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：

  (S,S)-ethylene(Ind)2ZrMe2 、 以 氘代苯 为溶剂， 生成 rac-(ethylenebis(indenyl))ZrMe(MeB(C6F5)3)
  参考文献：
  名称：

  Interpreting “Acidity” as a Global Property Controlling Comonomer Reactivity in Olefin Polymerization

  摘要：

  A possible rationale for the different catalytic behaviors of systems based on rac-(ethylenebis(1-indenyl))zirconium dichloride (rac-EBIZrCl2), rac-(ethylenebis(1-indenyl))hafnium dichloride (rac-EBIHfCl2), and rac-(isopropylidenebis(1-indenyl))zirconium dichloride (rac-iPrBIZrCl(2)) toward ethene-styrene copolymerization has been sought by studying related active systems. For this purpose, the metallocene ion pairs (IPs) rac-EBIZrMe-MeB(C6F5)(3), rac-EBIHfMe-MeB(C6F5)(3), and rac-iPrBIZrMe-MeB(C6F5)(3) have been synthesized and their structures in solution explored with ROESY and pulsed gradient NMR spectroscopy. The energetics of dynamical processes relevant for catalysis that can be used as indicators of the cation acidity have been studied with variable-temperature NMR experiments and density functional theory (DFT). NMR experiments successfully provided IP structural details in solution and also indicated the presence of an intricate dynamic behavior for all the IPs. DFT results, instead, indicated quantitatively how changing the metal and/or the ancillary ligand bridge influences the energetics of the active species and modifies the reaction energy profile. The theoretical results also drew attention to the fact that finding a rationale for the ligand influence on the catalytic behavior of rac-EBIZrCl2/MAO and rac-iPrBIZrCl(2)/MAO in ethene-styrene copolymerization requires not only considering the steric effects but also determining how subtle changes in the ligand sphere affect the capability of the metal center to accept electrons from the counteranion or the olefins.

  DOI：

  10.1021/om400076k
• 作为产物：
  描述：

  二甲基镁 、 rac-ethanediyl-bis(1-indenyl)zirconium dichloride 以 1,4-二氧六环 、 乙醚 为溶剂， 以62%的产率得到(S,S)-ethylene(Ind)2ZrMe2
  参考文献：
  名称：

  Enantioselective methylalumination of α-olefins

  摘要：

  The ability of various enantiopure zirconocenes to catalyze the asymmetric methylalumination of allylbenzene has been tested. The enantioselectivity of an ethylene(Ind)(2)ZrCl2/MAO system is the same as that of authentic methyl cation generated with Ph3C+ from ethylene(Ind)(2)ZrMe2, confirming that the methyl cation is the active catalyst from ethylene(Ind)2ZrCl2/MAO. (C) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2007.06.028

文献信息

• Kinetics of Initiation, Propagation, and Termination for the [<i>rac</i>-(C₂H₄(1-indenyl)₂)ZrMe][MeB(C₆F₅)₃]-Catalyzed Polymerization of 1-Hexene
  作者：Zhixian Liu、Ekasith Somsook、Curtis B. White、Kimberly A. Rosaaen、Clark R. Landis

  DOI：10.1021/ja016072n

  日期：2001.11.1

  activity and termination mechanisms of metallocene-catalyzed polymerizations. Herein we report the application of quenched-flow kinetics, active site counting, polymer microstructure analysis, and molecular weight distribution analysis to the determination of fundamental rate laws for initiation, propagation, and termination for the polymerization of 1-hexene in toluene solution as catalyzed by the contact

  茂金属催化的 1-烯烃聚合提供了对关键聚合物属性的精细控制，例如分子量、多分散性、立构规整度和共聚单体掺入。在合成和发现新的催化剂和活化剂方面付出了巨大的努力，但催化过程的基本方面仍不清楚。例如，目前尚不清楚催化剂如何分布在活性位点和休眠位点之间，以及这种分布如何影响单体中传播速率的顺序，报告的值变化很大。同样，虽然已经为许多系统建立了平均分子量和单体之间的经验关系，但链终止的潜在机制尚不清楚。另一个引起强烈兴趣的领域是离子对在控制茂金属催化聚合的活性和终止机制中的作用。在此，我们报告了淬火流动动力学、活性位点计数、聚合物微观结构分析和分子量分布分析在确定 1-己烯在甲苯溶液中催化聚合的引发、传播和终止的基本速率定律中的应用通过接触离子对，[rac-(C(2)H(4)(1-indenyl)(2))ZrMe][MeB(C(6)F(5))(3)] (1) over -10 到 50 摄氏度的温度范围。生产高度全同立构