meso-[Zr(1-Me2Si(3-η5-C9H5Et)2)Cl2] | 891189-41-6

• 英文名称: meso-[Zr(1-Me2Si(3-η5-C9H5Et)2)Cl2]
• 英文别名: rac-[Zr{1-Me₂Si(3-η⁵-C₉H₅Et)₂}Cl₂]；[Zr(1-Me2Si(3-η5-C9H5Et)2)Cl2]
• CAS: 891189-41-6；891189-42-7
• 化学式: C₂₄H₂₆Cl₂SiZr
• 分子量: 504.686
• InChiKey: MLZCKVRRDUEWBH-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

• 作为反应物：
  描述：

  meso-[Zr(1-Me2Si(3-η5-C9H5Et)2)Cl2] 、 氢气 在 platinum(IV) oxide 作用下， 以 四氢呋喃 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 36.0h， 以89%的产率得到rac-[Zr(1-Me₂Si{3-Et-(η⁵-C₉H₉)₂})Cl₂]
  参考文献：
  名称：

  走向对ansa-双（茚基）锆茂新烯在乙烯聚合反应中的活性的预测：立体化学和茚基部分氢化的影响。

  摘要：

  已对rac-和meso- [Zr {1-Me2 Si（3-η5-C9 H5 Et）2} Cl2]（rac-和meso-1）及其氢化形式（rac -和meso-2）了解配体的作用，并指导用于乙烯聚合的更具活性的ansa-双（茚基）锆茂金属的配体设计。制备了rac-ansa-锆茂金属rac- [Zr（1-Me2 Si {3-Et-（η5-C9 H9）} 2）Cl2]（rac-2），并已通过NMR光谱和元素分析对其进行了全面表征。rac-2的分子结构也已通过单晶XRD确定。在乙烯聚合中分析了催化剂的行为，获得了rac-1及其氢化形式rac-2更高的活性。已经通过计算研究评估了立体化学和茚基配体的氢化对实验活性的影响。沿着反应途径的差异主要由催化中间体的相对稳定性的变化决定。在甲苯作为溶剂的情况下进行的混合密度泛函B3LYP研究表明，rac形式比内消旋形式产生更多的活性物种。与内消旋形式相比，外消

  DOI：

  10.1002/cplu.201500008
• 作为产物：
  描述：

  Li2(1-Me2Si(3-C9H5Et)2) 、 氯化锆(IV) 以 乙醚 、 甲苯 为溶剂， 以30%的产率得到meso-[Zr(1-Me2Si(3-η5-C9H5Et)2)Cl2]
  参考文献：
  名称：

  Activation process of 3-alkyl-substituted ansa-bis(indenyl) zirconocenes by MAO

  摘要：

  The ansa-indene compound {1-Me2Si(3-C9H6Et)(2)} (1) was prepared by alkylation of the unsubstituted ansa-indene. This compound was converted. by reaction with nBuLi, to the dilithium compound [Li-2{1-Me2Si(3-C9H5Et)(2)}] (2). ansa-Zirconocene [Zr{1-Me2Si(3-eta(5)-C9H5Et)(2)}Cl-2] (3) was prepared by the reaction of ZrCl4 with 2 in ether/toluene at -78 degrees C. The molecular structure of meso-3 was determined by single crystal X-ray diffraction studies. The ansa-zirconocene 3 exhibits a greater activity in ethylene polymerization than reference complexes such as [Zr{1-Me2Si(eta(5)-C9H6)(2)}Cl-2] and [Zr{1-C2H4(eta(5)-C9H5)(2)}Cl-2] and, in addition, it maintained a reasonable level of activity after 12h of contact with MAO solution. Furthermore, the different elementary steps in the activation process of ethylene polymerization for substituted complexes [Zr{1-Me2Si(3-eta(5)-C9H5R)(2)}Cl-2] (R=Et 3, Me 4, nPr 5 and nBu 6) by commercial methylaluminoxane (MAO) have been studied by UV-vis spectroscopy. Addition of MAO in large excess ([Al]/[Zr] = 2000) at -78 degrees C yields a previously unreported intermediate in the activation process of metallocenes: this intermediate has an absorption band centered at lambda = 639 nm. We report here the influence of the type of catalyst, ring substitution, type of cocatalyst and addition of THF on the activation process of these metallocenes. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2006.07.041