| 161471-51-8

• CAS: 161471-51-8
• 化学式: C₂₅H₂₂ClNTi
• 分子量: 419.789
• InChiKey: MXZYYHFIXHUTBE-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：

  1,1-bis(η-cyclopentadienyl)titanaindan 、 1-氯-4-异氰基苯 以 乙醚 为溶剂， 以62%的产率得到
  参考文献：
  名称：

  Kinetics and Mechanism of the Reductive Elimination of Cyclic Titanocene Iminoacyls

  摘要：

  1,1-Dicyclopentadienyltitanaindan (1)reacts with isocyanides (RNC) to give cyclic iminoacyl complexes 2 (R = t-Bu) and 5a-e (R = p-R'C6H4, R' = Et(2)N, MeO, Me, H, and Cl) where the isocyanide has inserted into the Ti-CH2 bond. The X-ray crystal structure of 2 has been determined. Complex 2 crystallizes in a monoclinic space group P2(1) with a = 14.353(1), b = 8.556(2), c = 15.652(2) Angstrom; beta = 88.95(5); and Z = 4. Compounds 2 and 5a-e decompose in solution with formation of imines and paramagnetic Ti species. The decomposition follows first-order kinetics, with Delta C-double dagger = 24.5 +/- 0.2 Kcal mol, Delta H-double dagger = 24.3 +/- 0.2 Kcal mol, and Delta S-double dagger = -0.4 +/- 2 eu in the case of 2. The rate of imine elimination depends on the nature of the substituent on the nitrogen atom, higher rates are observed for electron-withdrawing substituents (Hammet theta = +1.59 +/- 0.04 for 5a-e), and the rate is little affected by the solvent or by the presence of PMe(3). These results are consistent with a concerted reductive elimination mechanism that initially leads to an unstable eta(1)-imine complex which subsequently converts to the observed products.

  DOI：

  10.1021/om00004a066