[ethylenebis(η(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride | 168640-28-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: [ethylenebis(η(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride
• 英文别名: 2-[2-(4,5,6,7-tetrahydroinden-2-id-2-yl)ethyl]-4,5,6,7-tetrahydroinden-2-ide;titanium(4+);dichloride
• CAS: 168640-28-6
• 化学式: C₂₀H₂₄Cl₂Ti
• 分子量: 383.197
• InChiKey: JZXFTMIVSGYXPT-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.33
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  [ethylenebis(η(5)-2-indenyl)]titanium dichloride 、 氢气 在 platinum(IV) oxide 作用下， 以 四氢呋喃 为溶剂， 以42%的产率得到[ethylenebis(η(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride
  参考文献：
  名称：

  Synthesis of ansa-Titanocenes from 1,2-Bis(2-indenyl)ethane and Structural Comparisons in the Catalytic Epoxidation of Unfunctionalized Alkenes

  摘要：

  Novel ansa-titanocene dichlorides have been prepared from 1,2-bis(2-indenyl)ethane (10). Treatment of the dilithio salt of 10 with either methyl iodide or benzyl bromide gives the corresponding dialkylated bis(indene) in high yield. Titanium complexation of the dimethyl and dibenzyl bis(indene) derivatives affords [ethylenebis[(eta(5)-1-methyl-2-indenyl)]titanium dichloride(14) and [ethylenebis[(eta 5-1-benzyl-2-indenyl)]titanium dichloride(15), respectively. In each case, the ansa-titanocene is obtained as a mixture of meso and racemic isomers. Treatment of the dilithio salt of 10 with trimethylsilyl chloride results in a mixture of bis(trimethylsilyl) derivatives. Attempted titanium complexation of the silylated bis(indene) mixture results in an intramolecular oxidative coupling of the C(3) and C(3') positions to yield a trans-6,7-dihydroindeno[2,1-c]fluorene derivative, 16. [Ethylenebis(eta(5)-2-indenyl)]titanium dichloride (9) is hydrogenated to yield tethylenebis(eta(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride (17). The crystal structures of rac-l4 and 17 were determined by X-ray crystallography and are presented. Examination of ethylene-bridged bis(2-indenyl) ansa-titanocenes as catalysts for the epoxidation of unfunctionalized alkenes was conducted using the representative titanocenes 9, 14, 15, and 17. The catalytic ability of this new class of. ansa-titanocenes in the epoxidation study was found in some cases to exceed the activity of existent titanocene complexes.

  DOI：

  10.1021/om00008a021
• 作为试剂：
  描述：

  5-氧代-5-苯基戊腈 在 三甲基氯硅烷 、 [ethylenebis(η(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride 、 三乙胺盐酸盐 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以91.3%的产率得到
  参考文献：
  名称：

  TiIII 催化的丙烯醛型 Umpolung 的机制：催化剂控制的自由基反应

  摘要：

  钛 (III) 催化的酮和腈之间的交叉偶联提供了 α-羟基酮的有效立体选择性合成。介绍了对该反应的详细机理研究，其中涉及多种方法的组合，如 EPR、ESI-MS、X 射线、原位红外动力学和 DFT 计算。我们的研究结果表明，CC 键的形成是周转限制性的，并且由涉及两种钛 (III) 物种的催化剂控制的自由基组合发生。静止状态被确定为阳离子二茂钛-腈复合物，并阐明了添加 Et3N·HCl 对产率和对映选择性的有益影响：氯配位引发自由基偶联。这些结果对于理解钛 (III) 催化和其他金属催化自由基反应具有重要意义。

  DOI：

  10.1021/jacs.5b09223

文献信息

• Synthesis of ansa-Titanocenes from 1,2-Bis(2-indenyl)ethane and Structural Comparisons in the Catalytic Epoxidation of Unfunctionalized Alkenes
  作者：Shawn R. Hitchcock、Janelle J. Situ、Jonathan A. Covel、Marilyn M. Olmstead、Michael H. Nantz

  DOI：10.1021/om00008a021

  日期：1995.8

  Novel ansa-titanocene dichlorides have been prepared from 1,2-bis(2-indenyl)ethane (10). Treatment of the dilithio salt of 10 with either methyl iodide or benzyl bromide gives the corresponding dialkylated bis(indene) in high yield. Titanium complexation of the dimethyl and dibenzyl bis(indene) derivatives affords [ethylenebis[(eta(5)-1-methyl-2-indenyl)]titanium dichloride(14) and [ethylenebis[(eta 5-1-benzyl-2-indenyl)]titanium dichloride(15), respectively. In each case, the ansa-titanocene is obtained as a mixture of meso and racemic isomers. Treatment of the dilithio salt of 10 with trimethylsilyl chloride results in a mixture of bis(trimethylsilyl) derivatives. Attempted titanium complexation of the silylated bis(indene) mixture results in an intramolecular oxidative coupling of the C(3) and C(3') positions to yield a trans-6,7-dihydroindeno[2,1-c]fluorene derivative, 16. [Ethylenebis(eta(5)-2-indenyl)]titanium dichloride (9) is hydrogenated to yield tethylenebis(eta(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride (17). The crystal structures of rac-l4 and 17 were determined by X-ray crystallography and are presented. Examination of ethylene-bridged bis(2-indenyl) ansa-titanocenes as catalysts for the epoxidation of unfunctionalized alkenes was conducted using the representative titanocenes 9, 14, 15, and 17. The catalytic ability of this new class of. ansa-titanocenes in the epoxidation study was found in some cases to exceed the activity of existent titanocene complexes.