| 177431-18-4

• CAS: 177431-18-4
• 化学式: C₁₄H₁₇Zr*C₁₉H₃BF₁₅
• 分子量: 803.533
• InChiKey: RRSQQMACYAPRNB-UHFFFAOYSA-N

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：

  、 三(五氟苯基)硼烷 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Zirconocene Allyl Complexes:  Dynamics in Solution, Reaction with Aluminum Alkyls, B(C₆F₅)₃-Induced Propene Insertion, and Density-Functional Calculations on Possible Formation and Reaction Pathways

  摘要：

  The complex (C5H5)(2)Zr(Me)(methallyl) (1) was prepared and studied as a model for Zr-bound allyl species which are likely to arise in zirconocene-based polymerization systems. 1 undergoes allyl-alkyl exchange with trimethyl aluminum (TMA) or with methyl alumoxane (MAO) at rates that are proportional to the Al concentration, but remain 1-2 orders of magnitude below those of typical olefin insertions. Its perfluorotriphenylborane adduct 2, i.e., the contact ion pair (C5H5)(2)Zr(methallyl)+H3CB(C6F5)(3)(-), has been characterized with regard to the rearrangement dynamics of its allyl ligand. Propene reacts with 2, at rates which are substantially lower again than those of cationic Zr-alkyl species, under insertion between Zr and one of the allylic termini. Scrambling of deuterium from an allylic CD2 terminus over several C atom positions next to the unsaturated chain end indicates rather extensive metal migration within an initial olefin insertion product. Density-functional calculations indicate that insertion of propene directly into an eta(3)-coordinated Zr-allyl unit occurs with lower activation energy than insertion into an eta(1)-bound Zr-allyl species and that the lowest-energy pathway for the reactivation of a cationic zirconocene allyl species is its reconversion to the corresponding Zr-alkyl species by molecular hydrogen.

  DOI：

  10.1021/om9906058