CpTiCl2(2,4-Me2C4H2N) | 1092072-66-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: CpTiCl2(2,4-Me2C4H2N)
• 英文别名: cyclopenta-1,3-diene;2,4-dimethylpyrrol-1-ide;titanium(4+);dichloride
• CAS: 1092072-66-6
• 化学式: C₁₁H₁₃Cl₂NTi
• 分子量: 278.017
• InChiKey: MURIDCQFCFHKRS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -3.33
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  三氯一茂钛 、 lithium 2,4-dimethylpyrrolide 以 正己烷 为溶剂， 以68%的产率得到CpTiCl2(2,4-Me2C4H2N)
  参考文献：
  名称：

  Synthesis and Structural Analysis of (Cyclopentadienyl)(pyrrolide)titanium(IV) Complexes and Their Use in Catalysis for Olefin Polymerization

  摘要：

  Cp*TiCl2,(L) [L = C4H4N (1), 2,5-Me2C4H2,N(2), 2,4-Me2C4HN (3), 2,4-Me-2,-3-EtC4HN (4)], Cp*TiCl(2A-Me,-3-EtC4HN)2 (5), and Cp*Ti(C4H4N)3 (6) were prepared by treating Cp*TiCl3 with the corresponding lithium salts in toluene or n-hexane. The structures of 3-6 determined by X-ray crystallography indicate that the complexes have a distorted tetrahedral geometry around Ti, and the nitrogen atom binds to Ti in an eta(l) fashion. The dimethyl analogues Cp*TiMe2,,(L) [L = C4H4N (7), 2.5-Me2C4H2,N (8)] could be prepared by adopting a route that involves in situ generation of Cp*Ti(CI)Me,. prepared by the reaction of Cp*TiCl3 with 2.0 equiv of MeLi in Et2O, and the subsequent treatment with the corresponding lithium salts. The Cp analogues CpTiCl2,(L) [L = C4H4N (9), 2,5-Me2C4H2N (10), 2.4-Me2C4H2,N (11), 2,4-Me-2-3-EtC4HN (12)] were also prepared by treating CpTiCl3 with the corresponding lithium salts in Et2O or n-hexane. The crystallographic analyses of 9-11 indicate that the dimethylpyrrolide ligand in 10 coordinates to Ti in eta(5) mode, whereas the nitrogen atom in the pyrrolide ligand (in complexes 9 and 11) binds to Ti in an eta(l) fashion (a bonding in addition to T donation). These complexes (1-4, 7-12) exhibited moderate catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO), and the activities were highly affected by the substituent on the pyrrolide ligand. In the polymerization using a series of dichloro complexes, the Cp*-pyrrolide analogue I exhibited the highest catalytic activity, and ail increase in the steric bulk led to the decrease in activity, whereas the activity of the Cp analogues increased upon increasing the steric bulk in the pyrrolide ligand. The dimethyl complexes (7, 8) exhibited notable catalytic activities in the presence of MAO, and the activities increased in the presence of (Bu3Al)-Bu-i/[Ph3C][B(C6F5)(4)] cocatalyst in place of MAO. The resultant polymers possessed unimodal molecular weight distributions. These complexes also exhibited moderate catalytic activities for syndiospecific styrene polymerization, and the activities of the Cp* analogues increased at high temperature.

  DOI：

  10.1021/om800713t