| 500552-76-1

• CAS: 500552-76-1
• 化学式: C₁₇H₂₇NSiZr
• 分子量: 364.718
• InChiKey: QBDOWZYESGJHTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  二甲基硅基双(2-甲基-4-苯基茚定基)二氯化锆 、 甲基锂 以 not given 为溶剂， 生成
  参考文献：
  名称：

  带有ansa酰胺基官能化的半三明治复合物和甲基铝氧烷的烷烃的催化热和光诱导CH和CC活化反应

  摘要：

  在文献中，烷烃的大多数脱氢反应被描述为环辛烷的CH活化反应。已发现CHA活化反应的最佳结果是MAO活化的茂金属络合物与环辛烷在300°C以上的温度下反应。 Ind'Si（Me）2NtBuMCl2（Ind'=单取代的茚基）类型的ansa酰胺基官能化半三明治化合物的应用；CH和CC活化反应的M = Ti，Zr，Hf）在文献中是完全未知的。 与环辛烷和第4组金属的茂金属配合物的脱氢反应相反，其中茂茂锆配合物给出的TONs高于二茂钛配合物，而ansa酰胺基官能化钛配合物给出的TONs则高出相应的Zr或Hf配合物两倍以上。ansa酰胺基官能化的配体会增加Ti络合物的TON，降低Zr络合物的TON。 与茂金属配合物相反，钛的ansa酰胺基官能化的二氯化物配合物也比相应的Zr配合物具有更高的活性。已知有机金属钛，锆和ha（IV）化合物的光解可产生M（III）自由基。与相应的Zr和Hf金属化合物相比，活性Ti金属中心的形成更容易。

  DOI：

  10.1016/j.jorganchem.2009.06.018

文献信息

• Indenyl-amido titanium and zirconium dimethyl complexes: improved synthesis and use in propylene polymerization
  作者：Luigi Resconi、Isabella Camurati、Cristiano Grandini、Marilisa Rinaldi、Nicoletta Mascellani、Orazio Traverso

  DOI：10.1016/s0022-328x(02)01853-3

  日期：2002.12

  The synthesis of a series of indenyl amido titanium dimethyl complexes, by means of the direct synthesis from the ligand, a 2-fold excess of MeLi, and TiCl4 is reported. The H-1 NMR spectra of the complexes show a quartet structure for the metal-bound methyl groups, due to through-metal proton-proton coupling. Coupling of Ti-methyl protons with protons on the Cp ring is also revealed by COSY 2D-NMR. The performance of the Ti complexes in propylene polymerization, including [Me2Si(Me4C5)(t-BuN)]TiMe2 (1-TiMe2), [Me2Si(Ind)(t-BuN)]TiMe2 (2-TiMe2) and six other methyl titanium complexes bearing substituted indenyl ligands, has been investigated with different cocatalysts and at different polymerization temperatures and propylene concentrations. All complexes produce amorphous polypropylene (am-PP). The catalytic activity and molecular weight strongly depend on the substitution of the Cp ring: 2-TiMe2 gives polymers of lower molecular weight, while the presence of a methyl group in position 2 (as in 3-TiMe2) determines up to 4-fold increase in molecular weight. The type of cocatalyst influences mainly the catalytic activity, the borates being better activators than MAO, but also molecular weight, with again the borates giving higher molecular weights than MAO. 5-TiMe2-Ph3CB(C6F5)(4) shows an overall activation energy of polymerization of 7.35 kcal mol(-1). The rate of chain release is first order in monomer. The following activation energies for overall chain release have been calculated: DeltaDeltaE(double dagger) 2-TiMe2 = 3.4 kcal mol(-1), DeltaDeltaE(double dagger) 5-TiMe2 = 3.8 kcal mol(-1), AAET 3-TiMe2 = 6.3 kcal mol(-1). Even if all the polymers produced are amorphous, 2-TiMe2 and 5-TiMe2 show a microstructure unbalanced towards isotacticity, while 3-TiMe2, 6-TiMe2 and 8-TiMe2 are syndiotactic-enriched. Chiral induction comes mainly from a weak enantiomorphic site control. (C) 2002 Elsevier Science B.V. All rights reserved.