methylene[(9-(2,7-di-tert-butyl)fluorenyl-2-(1,3-dimethyl)cyclopentadienyl)]zirconium dichloride | 760993-54-2

• 英文名称: methylene[(9-(2,7-di-tert-butyl)fluorenyl-2-(1,3-dimethyl)cyclopentadienyl)]zirconium dichloride
• CAS: 760993-54-2
• 化学式: C₂₉H₃₄Cl₂Zr
• 分子量: 544.719
• InChiKey: ACEABJGZFVPBSP-UHFFFAOYSA-L

反应信息

• 作为产物：
  描述：

  氯化锆(IV) 、 2,7-di-tert-butyl-9-(2,5-dimethyl-cyclopentadienylmethyl)-9-H-fluorene 在 n-C₄H₉Li 作用下， 以 正己烷 为溶剂， 以47%的产率得到methylene[(9-(2,7-di-tert-butyl)fluorenyl-2-(1,3-dimethyl)cyclopentadienyl)]zirconium dichloride
  参考文献：
  名称：

  Syntheses of methylene-bridged ansa-zirconocene complexes and copolymerization studies of ethylene and norbornene

  摘要：

  Methylene-bridged ansa-metallocene complexes bearing substituents on the cyclopentadienyl (Cp) and fluorenyl (Flu) moieties, namely methylene[9-(2,7-di-tert-butyl)fluorenyl(2-(1,3-dimethylcyclopentadienyl))]zirconium dichloride (1a) and its analogue, methylene[(9-(2,7-di-tert-butyl)fluorenyl(2-(1-methyl-3-phenyl)cyclopentadienyl))]zirconium dichloride (2a), have been prepared from (2,7-di-tert-butyl)-9-prop-2-ynyl-9H-fluorene (2). This procedure includes the use of 3-bromo-1-propyne which affords the methylene bridging unit by way of an intermolecular Pauson-Khand reaction in which norbornadiene and a pendant alkyne cyclize to form a ring that later becomes a substituted cyclopentadienyl group. Ethylene-norbornene (E-N) copolymerization was then carried out using these new complexes (1a and 1b) in the presence of methylaluminoxane (MAO) as a cocatalyst; these activities can be compared to that of isopropylene[9-fluorenyl-cyclopentadienyl]zirconium dichloride (3a). The activity of catalyst 1a was comparable to that of 3a but much higher than that of 2a. In addition, 1a shows higher norbornene insertion performance, and gives an E-N copolymer with a higher glass transition temperature (T-g) than 2a under identical conditions; both 1a and 2a give a lower T-g polymer than 3a does. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2004.05.015