{Me₂C-(3,6-tBu₂Flu)(3-tBu-5-MeC₅H₂)}ZrCl₂ | 288614-60-8

• 英文名称: {Me₂C-(3,6-tBu₂Flu)(3-tBu-5-MeC₅H₂)}ZrCl₂
• 英文别名: dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride
• CAS: 288614-60-8
• 化学式: C₃₄H₄₄Cl₂Zr
• 分子量: 614.853
• InChiKey: QNTGZKCQNINPDN-UHFFFAOYSA-L

反应信息

• 作为反应物：
  描述：

  {Me₂C-(3,6-tBu₂Flu)(3-tBu-5-MeC₅H₂)}ZrCl₂ 、 甲基锂 以 乙醚 为溶剂， 以82%的产率得到{Me₂C(3,6-tBu₂-Flu)(3-tBu-5-Me-Cp)}ZrMe₂
  参考文献：
  名称：

  高度等选择性锆茂的离散离子络合物。溶液动力学，三甲基铝加合物及其在丙烯聚合中的意义

  摘要：

  Discrete ionic complexes belonging to two main families of highly isoselective polymerization zirconocene ;systems, C-1-symmetric {Cp/Flu} (a,b) and C-2-symmetric {SBI} (c) systems, have been scrutinized. The ion pair reorganization processes for inner-sphere ion pairs (ISIPs) 3a,b-MeB(C6F5)(3), 3c-MeB(C6F5)(3), and 3c-MeAl(C6F5)(3) and for the outer-sphere ion pair (OSIP) AlMe3 adducts [6b,c](+)[B(C6F3)(4)](-), quantified by dynamic NMR analysis, were found to feature lower activation barriers for the {SBI}-based systems in comparison to those for the {Cp/Flu}-based congeners. The higher electrophilic character of the {Cp/Flu}-based cationic systems was corroborated by UV/vis spectroscopy studies coupled with TD-DFT calculations. These fundamental differences between the ionic systems of the two metallocene families are discussed in light of their respective propylene polymerization performances, and reasons for the higher productivity of {SBI} systems in comparison to {Cp-Flu} systems are proposed.

  DOI：

  10.1021/acs.organomet.5b00965