[(η5-pentamethylcyclopentadienyl)Ti((cyclopentyl)7Si7O9(OSiMe3)O2)]B(C6F5)4 | 1202038-87-6

• 英文名称: [(η5-pentamethylcyclopentadienyl)Ti((cyclopentyl)7Si7O9(OSiMe3)O2)]B(C6F5)4
• CAS: 1202038-87-6
• 化学式: C₂₄BF₂₀*C₄₈H₈₇O₁₂Si₈Ti
• 分子量: 1807.82
• InChiKey: RRKOWVYMPVQKQS-OGFPXNSMSA-N

反应信息

• 作为反应物：
  描述：

  [(η5-pentamethylcyclopentadienyl)Ti((cyclopentyl)7Si7O9(OSiMe3)O2)]B(C6F5)4 、 N,N-二甲基苯胺 以 甲苯 为溶剂， 生成 [(η5-pentamethylcyclopentadienyl)Ti(N,N-dimethylaniline-κ-N)((cyclopentyl)7Si7O9(OSiMe3)O2)]B(C6F5)4
  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：

  三苯碳四(五氟苯基)硼酸盐 、 syn-[(η5-pentamethylcyclopentadienyl)TiMe((cyclopentyl)7Si7O9(OSiMe3)O2)] 以 甲苯 为溶剂， 以83%的产率得到[(η5-pentamethylcyclopentadienyl)Ti((cyclopentyl)7Si7O9(OSiMe3)O2)]B(C6F5)4
  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