(pentamethylcyclopentadienyl)(π-η(5):σ-η(1)-tetramethylfulvene)phenylzirconium | 105501-02-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (pentamethylcyclopentadienyl)(π-η(5):σ-η(1)-tetramethylfulvene)phenylzirconium
• 英文别名: Cp'Zr(Ph)(η1:η5-CH2C5Me4)
• CAS: 105501-02-8
• 化学式: C₂₆H₃₄Zr
• 分子量: 437.78
• InChiKey: DAFRLTWLDDZFDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.09
• 重原子数：
  27.0
• 可旋转键数：
  1.0
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (pentamethylcyclopentadienyl)(π-η(5):σ-η(1)-tetramethylfulvene)phenylzirconium 在 氢气 作用下， 以 Petroleum ether 为溶剂， 生成 Cp'2Zr(H)Ph
  参考文献：
  名称：

  Miller, Frederick D.; Sanner, Robert D., Organometallics, 1988, vol. 7, # 4, p. 818 - 825

  摘要：

  DOI：
• 作为产物：
  描述：

  Cp'2Zr(H)Ph 以 苯 为溶剂， 以90%的产率得到(pentamethylcyclopentadienyl)(π-η(5):σ-η(1)-tetramethylfulvene)phenylzirconium
  参考文献：
  名称：

  Miller, Frederick D.; Sanner, Robert D., Organometallics, 1988, vol. 7, # 4, p. 818 - 825

  摘要：

  DOI：

文献信息

• Preparation of (Cp*) {C5Me4CH2B(C6F5)3}ZrPh, a novel zwitterionic single-component alkene polymerisation catalyst
  作者：Xuejing Song、Manfred Bochmann

  DOI：10.1016/s0022-328x(97)00389-6

  日期：1997.1

  B(C6F5)3 reacts with the fulvene complex (pentamethylcyclopentadienyl)(π-η5:σ-η1-tetramethylfulvene)phenylzirconium (Cp*FvZrPh) (I) selectively under attack at the fulvene-CH2 group to form the highly sensitive zwitterionic complex (Cp*)(C5Me4CH2-B(C6F5)3}ZrPh (II). Mixtures of I with either B(C6F5)3 or [CPh3][B(C6F5)4 are highly active for the polymerisation of ethene over a wide range of temperatures

  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。
• Organometallic thermochemistry. Metal hydrocarbyl, hydride, halide, carbonyl, amide, and alkoxide bond enthalpy relationships and their implications in pentamethylcyclopentadienyl and cyclopentadienyl complexes of zirconium and hafnium
  作者：Laurel E. Schock、Tobin J. Marks

  DOI：10.1021/ja00231a020

  日期：1988.11
• 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.
• Schock, Laurel E.; Brock, Carolyn P.; Marks, Tobin J., Organometallics, 1987, vol. 6, # 2, p. 232 - 241
  作者：Schock, Laurel E.、Brock, Carolyn P.、Marks, Tobin J.

  DOI：——

  日期：——