ethylene-1-(9-fluorenyl)-2-{1-[3-(2-methylbenzyl)indenyl]} zirconium dichloride | 1610803-36-5

• 英文名称: ethylene-1-(9-fluorenyl)-2-{1-[3-(2-methylbenzyl)indenyl]} zirconium dichloride
• CAS: 1610803-36-5
• 化学式: C₃₂H₂₆Cl₂Zr
• 分子量: 572.688
• InChiKey: SKDRGWORMPXZCY-UHFFFAOYSA-L

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：

  9-(2-溴乙基)-9h-芴 、 邻甲基氯化苄 、 氯化锆(IV) 、 茚 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以0.21 g的产率得到ethylene-1-(9-fluorenyl)-2-{1-[3-(2-methylbenzyl)indenyl]} zirconium dichloride
  参考文献：
  名称：

  Ethylene-bridged C1-symmetric ansa-(3-R-indenyl)(fluorenyl) zirconocene complexes for propylene dimerization or polymerization: The effect of R group

  摘要：

  A series of ethylene-bridged C-1-symmetric ansa-(3-R-indenyl)(fluorenyl) zirconocene complexes 3a-i (R = 2[2-(4-methylphenyl)propyl], 3a; R = 2-[2-(3,5-dimethylphenyl)propyl], 3h; R = 2-(2-benzylpropyl), 3c; R = 2-methylbenzyl, 3d; R = 2-(2-cyclohexylpropyl), 3e; R = 2-[2-(1-cyclohexenyl)propyl], 3f; R = 2-(2-n-butylpropyl), 3g; R = cyclohexyl, 3h; R = Pr-i, 3i) were synthesized by a salt metathesis method and characterized by NMR spectroscopy, elemental analysis (or HRMS) and X-ray diffraction (3e and 3h). Upon activation with methylaluminoxane, most of these zirconocene complexes exhibited sufficient catalytic activities up to 2.5 x 10(5) g C-6/(mol-Zr.h) and high selectivities up to 99% toward propylene dimerization, affording 2-methyl-1-pentene as the major isomer which was confirmed by gas chromatography. Remarkably, the selectivity and activity of complexes 3a-i were significantly influenced by the structural features of the substituent on the 3-position of indenyl ring: a pendant aryl or alkyl group linked by a quaternary carbon bridge provided the complex with high selectivities in the range of 89.9-99.0% for 2-methyl-1-pentene and low to moderate catalytic activities; the lack of a quaternary carbon bridge within the substituent would lead to mainly polypropylenes of low molecular weight. The steric hindrance around the active metal center induced by the pendant group might be responsible for the catalytic dimerization behavior, and the presumed mechanism was discussed. In addition, for complexes 3h and 3i, the selectivity for propylene dimerization could also be enhanced with the increase of reaction temperature. Noticeably, most of these ansa-zirconocene complexes exhibit excellent thermal stability at 100 degrees C, which is important with regard to industrial application. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.03.019
• 作为试剂：
  描述：

  三聚丙烯 在 ethylene-1-(9-fluorenyl)-2-{1-[3-(2-methylbenzyl)indenyl]} zirconium dichloride 作用下， 反应 0.5h， 以14.0 mg的产率得到顺式-4-甲基-2-戊烯
  参考文献：
  名称：

  Ethylene-bridged C1-symmetric ansa-(3-R-indenyl)(fluorenyl) zirconocene complexes for propylene dimerization or polymerization: The effect of R group

  摘要：

  A series of ethylene-bridged C-1-symmetric ansa-(3-R-indenyl)(fluorenyl) zirconocene complexes 3a-i (R = 2[2-(4-methylphenyl)propyl], 3a; R = 2-[2-(3,5-dimethylphenyl)propyl], 3h; R = 2-(2-benzylpropyl), 3c; R = 2-methylbenzyl, 3d; R = 2-(2-cyclohexylpropyl), 3e; R = 2-[2-(1-cyclohexenyl)propyl], 3f; R = 2-(2-n-butylpropyl), 3g; R = cyclohexyl, 3h; R = Pr-i, 3i) were synthesized by a salt metathesis method and characterized by NMR spectroscopy, elemental analysis (or HRMS) and X-ray diffraction (3e and 3h). Upon activation with methylaluminoxane, most of these zirconocene complexes exhibited sufficient catalytic activities up to 2.5 x 10(5) g C-6/(mol-Zr.h) and high selectivities up to 99% toward propylene dimerization, affording 2-methyl-1-pentene as the major isomer which was confirmed by gas chromatography. Remarkably, the selectivity and activity of complexes 3a-i were significantly influenced by the structural features of the substituent on the 3-position of indenyl ring: a pendant aryl or alkyl group linked by a quaternary carbon bridge provided the complex with high selectivities in the range of 89.9-99.0% for 2-methyl-1-pentene and low to moderate catalytic activities; the lack of a quaternary carbon bridge within the substituent would lead to mainly polypropylenes of low molecular weight. The steric hindrance around the active metal center induced by the pendant group might be responsible for the catalytic dimerization behavior, and the presumed mechanism was discussed. In addition, for complexes 3h and 3i, the selectivity for propylene dimerization could also be enhanced with the increase of reaction temperature. Noticeably, most of these ansa-zirconocene complexes exhibit excellent thermal stability at 100 degrees C, which is important with regard to industrial application. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.03.019