[(η5-C5Me5)Ti(O-t-Bu)2Me] | 937784-85-5

• 英文名称: [(η5-C5Me5)Ti(O-t-Bu)2Me]
• 英文别名: [(η5-pentamethylcyclopentadienyl)Ti(O(t-Bu))2Me]
• CAS: 937784-85-5
• 化学式: C₁₉H₃₆O₂Ti
• 分子量: 344.374
• InChiKey: XJPBDWFQTBKMON-UHFFFAOYSA-N

计算性质

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

• 作为反应物：
  描述：

  [(η5-C5Me5)Ti(O-t-Bu)2Me] 、 三甲基铝 以 甲苯 为溶剂， 生成 [(η5-C5Me5)Ti(O-t-Bu)Me2]
  参考文献：
  名称：

  Pentamethylcyclopentadienylmethyltitanium Silsesquioxanes and Their Zwitterionic Complexes with Tris(pentafluorophenyl)borane

  摘要：

  Reaction of [(eta(5)-C5Me5)TiMe3] With [(c-C5H9)(7)Si8O12(OH)] (SIPOSS) or [(c-C5H9)(7)Si7O9(OSiMe3)(OH)(2))] (DIPOSS') affords stoichiornetrically the half-sandwich titanium-disiloxy-nicthyl complexes [(eta(5)-C5Me5){(c-C5H9)(7)Si8O12O}(2) TiMe (1) and [(eta(5)-C5Me5) (c-C5H9)(7)Si7O9(OSiMe3)-O-2}TiMe] (2), respectively. Compound 2 consists orthe two stercoisonlers possessing the (eta(5)-C5Me5) ligand and OSiMe3 group in sYn- (2a) and anti-position (2b). The more abundant 2a (2a/2b approximate to 2:1) was isolated by fractional crystallization. Compounds I and 2a reacted rapidly with B(C6F5)(3) to give zwitterionic Complexes [(eta(5)-C5Me5) (c-C5H9)(7)Si8O12O}(2)Ti]((+)) (mu-Me)B(C6F5)(3)]((-)) 3 and syn-[eta(5)- C5Me5){(c-C5H9)(7)Si7O9(OSiMe3)O-2}Ti]((+))[(mu-Me)B(C6F5)(3)]((-)) (4a), respectively. Infrared spectra proved that 3 and 4awere thermally stable in the solid state, and the structure of 4a was determined by X-ray single-crystal analysis. In contrast, H-1, C-13, and F-19 NMR spectra of 3 in toluene C7D8 revutled that it was completely dissociated into initial components at 25 'C; however, the features of 3 were dominating already at -35 degrees C. On the other hand, 4a was dissociated only slightly at 25 degrees C. Stable ionic complexes 7 and 8 were prepared by reacting [PhNHMe2](+)[B(C6F5)(4)](-) With 1 and 2, respectively. Both 7 and 8 contained the molecule PhNMe, coordinated to the titanium cation, and 8 consisted of thes ' wi-and ami-isorners 8a and 81) in abundances found for 2a/2b. Analogous reaction of 1 and 2 with [Ph3C](+)[B(C6H5)(4)](-) afforded in1pUre ionic complexes 9and 10. When dissolved in the presence of PhNMe2, the amine Coordinated to the titanium cations, thus reproducing complexes 7 and 8a/8b, identified by H-1 NMR spectra. All compounds 1-10 were inactive in polymerization of styrene to syndiotactic polymer. A low activity was achieved by adding of 2 equiv of AlMe3 to 3 or 4.

  DOI：

  10.1021/om9007345
• 作为产物：
  描述：

  [(η5-C5Me5)Ti(O-t-Bu)2Cl] 、 甲基锂 以 乙醚 、 甲苯 为溶剂， 以94%的产率得到[(η5-C5Me5)Ti(O-t-Bu)2Me]
  参考文献：
  名称：

  The first thermally stable half-sandwich titanium zwitterionic complex

  摘要：

  Thermally stable zwitterionic complex [(eta(5)-C5Me5)Ti(Ot-Bu)(2)]((delta+))[(mu-Me)B(C6F5)(3)]((delta-)) (5) was formed by mixing equimolar quantities of [(eta(5)-C5Me5)TiMe(Ot-Bu)(2)] and [B(C6F5)(3)]. The compound was recrystallized from hot toluene and has been stable so far for 1 year at ambient temperature in the solid state and in toluene solution. The H-1, F-19 and 1D NOESY NMR spectra in C6D6 solution proved the inner sphere ion pair structure of 5. The X-ray crystal structure of 5 revealed that the bridging methyl group is sigma-bonded to boron, and all its C-H bonds fulfil criteria for agostic bonding interaction with the titanium atom. In contrast to the stable solution in C6D6 compound 5 decomposed in CD2Cl2 solvent within hours at room temperature. (c) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2007.01.022