benzene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tris(2,3,4,5,6-pentafluorophenyl)-[(2,3,4,5-tetramethylcyclopenta-1,4-dien-1-yl)methyl]boranuide;zirconium(4+) | 190327-24-3

• 分子结构分类: 有机化合物
• 英文名称: benzene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tris(2,3,4,5,6-pentafluorophenyl)-[(2,3,4,5-tetramethylcyclopenta-1,4-dien-1-yl)methyl]boranuide;zirconium(4+)
• CAS: 190327-24-3
• 化学式: C₄₄H₃₄BF₁₅Zr
• 分子量: 949.765
• InChiKey: AEDXNETYQNMFNA-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

• 作为反应物：
  描述：

  丙酮 、 benzene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tris(2,3,4,5,6-pentafluorophenyl)-[(2,3,4,5-tetramethylcyclopenta-1,4-dien-1-yl)methyl]boranuide;zirconium(4+) 以 苯 为溶剂， 以84%的产率得到benzene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;propan-2-one;tris(2,3,4,5,6-pentafluorophenyl)-[(2,3,4,5-tetramethylcyclopenta-1,4-dien-1-yl)methyl]boranuide;zirconium(4+)
  参考文献：
  名称：

  两性离子茂锆的Cp *的丙酮和苯乙酮加合物[η 5 -C 5我4 CH 2 B（C 6 ˚F 5）3 ]的ZrC 6 ħ 5

  摘要：

  最近报道的两性离子复合物的Cp * [η 5 -C 5我4 CH 2 B（C 6 ˚F 5）3 ]的ZrC 6 ħ 5，1，1个当量丙酮或苯乙酮的快速反应以形成加合物的Cp * [η 5 -C 5我4 CH 2 B（C 6 ˚F 5）3 ]的Zr（C 6 H ^ 5）〔O C（CH 3）R（R = CH 3，图2a ;ç 6 ħ 5，2b）〜85％的产率。提出了有利于该任务的光谱证据；在每种情况下，还通过X射线结构分析确定了配合物的加合物性质。酮配位体结合在η 1周端上的方式（Zr的-O Ç角度接近线性的在174.2°和166.1°，图2a和2b中，分别地），从而允许一个π组分与Zr-O键合。与其他非两性离子型阳离子金属茂的短暂观察到的酮加合物不同，化合物2中的酮配体无论在热分解还是在过量酮的存在下都不会插入Zr-C键中。

  DOI：

  10.1021/om970066b
• 作为产物：
  描述：

  (pentamethylcyclopentadienyl)(π-η(5):σ-η(1)-tetramethylfulvene)phenylzirconium 、 三(五氟苯基)硼烷 以 甲苯 为溶剂， 以80%的产率得到benzene;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tris(2,3,4,5,6-pentafluorophenyl)-[(2,3,4,5-tetramethylcyclopenta-1,4-dien-1-yl)methyl]boranuide;zirconium(4+)
  参考文献：
  名称：

  新型两性离子单组分烯烃聚合催化剂（Cp *）{C 5 Me 4 CH 2 B（C 6 F 5）3 } ZrPh的制备

  摘要：

  B（C 6 ˚F 5）3种发生反应与富烯络合物（五甲基环戊二烯）（π-η 5：σ-η 1 -tetramethylfulvene基）苯基（CP * FvZrPh）（我）选择性下，在富烯-CH攻击2基团，形成高度敏感的两性离子复合物（CP *）{（C 5我4 CH 2 -B（C 6 ˚F 5）3 } ZrPh（II）。的混合物我带有B（C 6 ˚F 5）3或[器CPh 3] [B（C 6 F 5）4在很大的温度范围内对乙烯的聚合都具有很高的活性。

  DOI：

  10.1016/s0022-328x(97)00389-6

文献信息

• Intramolecular Ion−Ion Interactions in Zwitterionic Metallocene Olefin Polymerization Catalysts Derived from “Tucked-In” Catalyst Precursors and the Highly Electrophilic Boranes XB(C₆F₅)₂ (X = H, C₆F₅)
  作者：Yimin Sun、Rupert E. v. H. Spence、Warren E. Piers、Masood Parvez、Glenn P. A. Yap

  DOI：10.1021/ja970140h

  日期：1997.6.1

  The reactions of so called ''tuck-in'' permethyl zirconocene compounds Cp*(eta(5)-eta(1)-C5Me4CH2)ZrX (X = Cl (1a), C6H5 (1b), CH3 (1c)) with the highly electrophilic boranes HB(C6F5)(2) and B(C6F5)(3) are described. The products are zwitterionic olefin polymerization catalysts. Reactions with la and Ib yielded single products cleanly, but reactions with tuck-in methyl starting material Ic gave mixtures. Spectroscopic and structural studies showed that the electrophilic zirconium center in the product zwitterions was stabilized by a variety of mechanisms. In the products of reaction between 1a and 1b with HB(C6F5)(2), Cp*[eta(5) eta(1)-C5Me4CH2B(C6F5)(2)(mu-H)]ZrX (X = Cl (2a), 74%), C6H5 (2b, 62%)), the metal is chelated by a pendant hydridoborate moiety. Chloride product 2a was characterized crystallographically. In the reaction of B(C6F5)(3) with 1a, the fluxional zwitterionic product Cp*[eta(5)-C5Me4CH2B(C6F5)(3)]ZrCl (3a, 84%) is stabilized by a weak donor interaction between one of the ortho fluorine atoms of the -CH2B-(C6F5)(3) counterion and the zirconium center (Zr-F = 2.267(5) Angstrom). In the product of the reaction between 1b and B(C6F5)(3), Cp*[eta(5)-C5Me4CH2B(C6F5)(3)]ZrC6H5 (3b, 82%), a similar ortho-fluorine interaction was found in a yellow kinetic product (y-3b), which converted upon heating gently to a thermodynamic orange polymorph (o-3b) in which the zirconium center is compensated via an agostic interaction from an ortho C-H bond of the phenyl group and an interaction between the methylene group of the -CH2B-(C6F5)(3) counteranion. These compounds were both characterized by X-ray crystallography. Zwitterion o-3b reacts with H2 to form the zwitterionic hydride Cp*[eta(5)-C5Me4CH2B(C6F5)(3)]ZrH (4, 77%), characterized by NMR spectroscopy and X-ray crystallography to reveal a return to the ortho-fluorine mode of stabilization. Compounds 2a, 3a, o-3b, and 4 were all found to be active ethylene polymerization catalysts; the chloride derivatives required minimal amounts of methylaluminoxane (MAO) to alkylate the zirconium center. Polymerization data are discussed in light of the structural findings for the catalysts employed.