(Me2C(fluo)(Cp))ZrCl2 | 130638-44-7

• 英文名称: (Me2C(fluo)(Cp))ZrCl2
• 英文别名: isopropyl(cyclopentadienyl)(9-fluorenyl)zirconiumdichloride；isopropylene[9-fluorenylcyclopentadienyl]zirconium dichloride；isopropylidene(cyclopentadienylfluorenyl)ZrCl2；(η5-C5H4)CMe2-η5-(C13H8)ZrCl2；[η5-cyclopentadienyl-dimethyl-η5-fluorenyl-methane zirconium (chloride)2]；[(fluorenyl-C(CH3)2-cyclopentadienyl)ZrCl2]；[ZrCl2(CMe2(cyclopentadienyl)(fluorenyl))]；Me2C(fluorenyl-cyclopentadienyl)ZrCl2；(Me2C(C5H4)(9-fluorenyl))ZrCl2；iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride
• CAS: 130638-44-7
• 化学式: C₂₁H₁₈Cl₂Zr
• 分子量: 432.504
• InChiKey: UFDDKDCNMRTHGQ-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：

  (Me2C(fluo)(Cp))ZrCl2 在 Li{BHEt₃} 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以58%的产率得到
  参考文献：
  名称：

  Bochmann, Manfred; Lancaster, Simon J.; Hursthouse, Michael B., Organometallics, 1993, vol. 12, # 12, p. 4718 - 4720

  摘要：

  DOI：
• 作为产物：
  描述：

  氯化锆(IV) 、 9-(1-(2,4-环五二烯-1-基)-1-甲基乙基)-9H-芴 在 正丁基锂 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.0h， 以40%的产率得到(Me2C(fluo)(Cp))ZrCl2
  参考文献：
  名称：

  原位活化：用茂金属二氯化物形成超高分子量间规聚丙烯的机会和限制

  摘要：

  合成了具有不同桥接基序（C 和 Si）的芴基环戊二烯基C s对称柄型茂金属（M = Zr，Hf）配合物I - IV，随后在丙烯的间规配位聚合中进行了检测。所有复合物活化原位用三异丁基铝（TIBA）和[PH 3 C] [B（C 6 ˚F 5）4，以突出的这样的好处（TrBCF）原位活化，导致与甲基铝氧烷 (MAO) 相比显着更高的分子量和显着提高的生产率。异丙叉桥联的二茂锆Ia (ZrCl 2 [Me 2 C(η 5 -Flu)(η 5 -Cp)]) 表现出高生产率 (80000 kg PP (mol cat h) -1 ) 和立构规整性 ([rrrr] up至 93%) 与中等分子量的聚丙烯 (PP)，而与相应的铪茂Ib (HfCl 2 [Me 2 C(η 5 -Flu)(η 5-Cp)]) 导致较低的生产率和立构规整性，但产生超高分子量聚丙烯 ( M w = 1100 kg mol –1

  DOI：

  10.1021/acs.organomet.1c00397

文献信息

• Structural Dichotomy in Single-Component Ziegler Catalyst Systems:  Characterization of Zr···F and Zr···C-Bonded Structural Types of Group 4 Metallocene [C₄H₆−B(C₆F₅)₃] Betaines
  作者：Marc Dahlmann、Gerhard Erker、Roland Fröhlich、Oliver Meyer

  DOI：10.1021/om0003741

  日期：2000.8.1

  exhibits internal (aryl)C−F···Zr coordination. A similar reaction sequence was observed during the addition of B(C6F5)3 to the parent (butadiene)zirconocene system 1:  at 213 K the kinetic Cp2Zr[(Z)-(1−3η),κC4-C4H6−B(C6F5)3] betaine product 14 is formed, which rapidly rearranges at temperatures above 253 K to yield the previously observed stable Cp2Zr[(E)-C4H6−B(C6F5)3] betaine system 2, which is characterized

  有机金属路易斯酸B（C 6 F 5）3加到（丁二烯）茂金属络合物5a和5b的末端CH 2基团上，得到ansa-茂金属甜菜碱系统[Me 2 Si（C 5 H 4）2 ] Zr [C 4 H 6 -B（C 6 F 5）3 ]（6a）和[Me 2 Si（3-MeC 5 H 3）2 ] Zr [C 4 H 6 -B（C6 F 5）3 ]（6b）分别以高收率获得。两种配合物均通过X射线衍射表征。它们都包含取代η 3 -烯丙基配体F的ë配置，并且它们表现出特性（邻芳基）C-F···Zr的相互作用稳定该偶极结构内的缺电子的金属中心。B（C 6 ˚F 5）3也增加之一丁二烯末端（小号-顺-η 4 -C 4 H ^ 6）[本人2 C（ç 5 ħ 4）（茚基）] Zr得到高产率的相应的ansa-茂金属[C 4 H 6 -B（C 6 F 5）3 ]甜菜碱络合物9的单一异构体。的X射线晶体结构分析9显示，在这种情况下（ż）-η
• Syndiospezif ische polymerisation von propylen: Modellverbindungen des typs (C13H8−nRnCMe2C5H4)Zr(H2CCHR′)(PMe3) (n = 0,2; R = H, Me; R′ = Me, Et)
  作者：Helmut G Alt、Roland Zenk

  DOI：10.1016/0022-328x(95)06094-d

  日期：1996.9

  One unbridged and three bridged zirconocene complexes, each of them bearing a cyclopentadienyl, fluorenyl, α-olefin and a PMe3 ligand have been prepared and characterized by 1H, 13C and 31P NMR spectroscopy. These model compounds illustrate the mechanism of olefin coordination and insertion at the active sites of syndiospecific homogeneous catalysts for the polymerization of propylene and 1-butene

  制备了一个未桥和三个桥的锆茂复合物，它们各自带有环戊二烯基，芴基，α-烯烃和PMe 3配体，并通过1 H，13 C和31 P NMR光谱表征。这些模型化合物说明了烯烃配位和间位特异性均相催化剂在丙烯和1-丁烯聚合反应活性位点上的插入机理。
• Ligand Mobility and Solution Structures of the Metallocenium Ion Pairs [Me₂C(Cp)(fluorenyl)MCH₂SiMe₃⁺···X⁻] (M = Zr, Hf; X = MeB(C₆F₅)₃, B(C₆F₅)₄)
  作者：Carlos Alonso-Moreno、Simon J. Lancaster、Joseph A. Wright、David L. Hughes、Cristiano Zuccaccia、Andrea Correa、Alceo Macchioni、Luigi Cavallo、Manfred Bochmann

  DOI：10.1021/om800486p

  日期：2008.11.10

  metallocene complexes (IPCF)M(Me)(CH2SiMe3) (M = Zr, Hf; IPCF = Me2C(C5H4)(C13H8)) were synthesized by the reaction of (IPCF)M(Me)Cl (M = Zr, Hf) with Me3SiCH2MgCl. The crystal structures of (IPCF)Zr(CH2SiMe3)2, (IPCF)HfMe2, and (IPCF)Zr(Me)Cl were determined by X-ray diffraction. The kinetics of site epimerization of the ion pairs (IPCF)M(CH2SiMe3)(μ-Me)B(C6F5)3 and [(IPCF)MCH2SiMe3+···B(C6F5)4−] (M = Zr

  混合烷基茂金属配合物（IPCF）M（Me）（CH 2 SiMe 3）（M = Zr，Hf; IPCF = Me 2 C（C 5 H 4）（C 13 H 8））的合成（IPCF）M（Me）Cl（M = Zr，Hf）和Me 3 SiCH 2 MgCl。通过X射线衍射确定（IPCF）Zr（CH 2 SiMe 3）2，（IPCF）HfMe 2和（IPCF）Zr（Me）Cl的晶体结构。离子对（IPCF）M（CH 2 SiMe 3）（μ-Me）B（C 6 F 5）3的位点差向异构动力学并通过变温NMR光谱研究了[（IPCF）MCH 2 SiMe 3 + ··B（C 6 F 5）4 - ]（M = Zr，Hf），而离子对的溶液基态结构[LZrCH 2 SiMe 3 + ... B（C 6 F 5）4 - ]（L = SBI，IPCF; SBI = rac -Me 2 Si（Ind）2）由19 F，1进行了实验探测。H
• Base-free cationic zirconium benzyl complexes as highly active polymerization catalysts
  作者：Manfred Bochmann、Simon J. Lancaster

  DOI：10.1021/om00027a012

  日期：1993.3

  Zirconium dibenzyl complexes CP2Zr(CH2Ph)2 (1a), (C5H4SiMea)2Zr(CH2Ph)2 (2a) rac-Et-(Ind)2Zr(CH2Ph)2 (3a), and i-Pr(Cp)(Flu)Zr(CH2Ph)2 (4a) react with [CPh3]+B(C6F5)4- (5) in toluene to give base-free cationic zirconium benzyl complexes of the type [CP'2Zr(CH2Ph)]+-B(C6F5)4-(1b-4b). The cationic complexes contain eta2-bonded benzyl groups; they are thermally significantly more stable than related methyl complexes, e.g. [Et(Ind)2Zr(CH3)]+, and catalyze the polymerization of ethene and propene at 1 bar of monomer pressure. The activities increase with temperature and are similar to or better than those of the corresponding CP'2ZrCl2/methylaluminoxane catalysts under comparable conditions; at 60-degrees-C 3b exhibits an activity of >21 000 kg of polypropene/[(mol of Zr).[C3H6].h]. The temperature dependence of the steroeregularity and the molecular weight distribution of polypropenes produced with 3b and 4b closely reflects that of polymers produced with methylaluminoxane-activated catalysts. More electron-deficient zirconium benzyl complexes are less active catalysts, with the polymerization activity for ethene decreasing for [CP2Zr(CH2Ph)]+ > [CpZr(CH2Ph)2]+ > [Zr(CH2Ph)3]+ >> Zr(Ch2Ph)4; polyethene produced with [Zr(CH2Ph)3]+ has a high molecular weight (M(w) = ca. 500 000, M(w)/M(n) = 2.8).
• Preparation and crystal structures of the complexes (η5-C5H4CMe2η5-C13H8) MCl2 (M  Zr, Hf) and their role in the catalytic formation of syndiotactic polypropylene
  作者：Abbas Razavi、Joseph Ferrara

  DOI：10.1016/0022-328x(92)83400-c

  日期：1992.9

  The reactions Of MCl4 (M = Zr, Hf) with the dilithium salt of 2-cyclopentadienyl-2-fluorenylpropane in pentane solution give the complexes (eta-5-C5H4CMe2-eta-5-C13H8)MCl2. NMR and X-ray diffraction data show that there are eta-5-bonded fluorenyl groups in these complexes. When activated with methytalumoxane both complexes catalyse the stereospecific polymerization of propylene to syndiotactic polypropylene.