Cp2ZrMe(pentafluorophenyl) | 219627-13-1

• 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: Cp2ZrMe(pentafluorophenyl)
• 英文别名: Cp2Zr(Me)(C6F5)；Cp2Zr(C6F5)Me；carbanide;cyclopenta-1,3-diene;1,2,3,4,5-pentafluorobenzene-6-ide;zirconium(4+)
• CAS: 219627-13-1
• 化学式: C₁₇H₁₃F₅Zr
• 分子量: 403.506
• InChiKey: BJXWGEZUVJBPQL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Cp2ZrMe(pentafluorophenyl) 、 六氟苯 以 氘代四氢呋喃 为溶剂， 生成 dicyclopentadienylmethylzirconium fluoride
  参考文献：
  名称：

  Generation of Perfluoropolyphenylene Oligomers via Carbon−Fluorine Bond Activation by Cp₂Zr(C₆F₅)₂:  A Dual Mechanism Involving a Radical Chain and Release of Tetrafluorobenzyne

  摘要：

  The thermal decomposition of Cp2Zr(C6F5)(2) in THF results in the slow formation of Cp2Zr(C6F5)F and tetrafluorobenzyne. The tetrafluorobenzyne is trapped by THF to give several products. The same reaction performed in the presence of durene or furan also results in the formation of Cp2Zr(C6F5)F and the respective Diels-Alder adducts of tetrafluorobenzyne. If Cp2Zr(C6F5)(2) is heated in the presence of C6F6, linear chains of perfluoroarenes are rapidly generated along with Cp2Zr(C6F5)F. The disappearance of Cp2Zr(C6F5)(2) is observed to slow dramatically after 30-80% completion, with the extent of reaction being inversely dependent on the concentration of C6F6. Dual mechanisms involving a rapid radical chain-and a slower tetrafluorobenzyne producing reaction are proposed to account for these observations.

  DOI：

  10.1021/ja991805d
• 作为产物：
  描述：

  以 not given 为溶剂， 生成 Cp2ZrMe(pentafluorophenyl)
  参考文献：
  名称：

  具有源自C 6 F 4 -1,2- [B（C 6 F 5）2 ] 2的新的弱配位阴离子的新型三苯甲基活化剂：合成，结构和烯烃聚合行为

  摘要：

  制备弱配位阴离子{C 6 F 4 -1,2- [B（C 6 F 5）2 ] 2（μ-OR）} -（R = CH 3，C 6 F 5）作为三苯甲基盐（2-OR）并具有充分的特征。与Cp 2 ZrMe 2的化学计量反应可生成二聚（3-OR）或单体（4-OR）金属茂离子。后者是用于乙烯聚合的高效助催化剂。

  DOI：

  10.1021/om0001974

文献信息

• Bifunctional Lewis Acids. Synthesis and Olefin Polymerization Chemistry of the 1,1-Di[bis(perfluorophenyl)boryl]alkenes RCHC[B(C₆F₅)₂]₂ (R = <i>t</i>-Bu, C₆H₅, C₆F₅)
  作者：Katrin Köhler、Warren E. Piers、Adam P. Jarvis、S. Xin、Y. Feng、A. M. Bravakis、Scott Collins、William Clegg、Glenn P. A. Yap、Todd B. Marder

  DOI：10.1021/om980259e

  日期：1998.8.1

  The synthesis and characterization, including crystallographic analysis, of the bifunctional boranes RCHC[B(C6F5)2]2 (R = t-C4H9, 1a; C6H5, 1b; C6F5, 1c) by regioselective hydroboration of the corresponding 1-boraalkynes using HB(C6F5)2 are reported herein. Compounds 1a and 1b have been screened as cocatalysts for ethylene polymerization in the presence of Cp2ZrMe2 (3) under a variety of conditions

  双官能硼烷的合成和表征，其中包括结晶学分析，RCH C [B（C 6 ˚F 5）2 ] 2（R =吨-C 4 ħ 9，图1A ;Ç 6 ħ 5，1B ;Ç 6 ˚F 5，本文报道了使用HB（C 6 F 5）2通过相应的1-硼烷炔的区域选择性氢硼化进行的1c）的报道。化合物1a和1b在多种条件下，在Cp 2 ZrMe 2（3）的存在下，已筛选出作为乙烯聚合的助催化剂。NMR光谱研究表明的Cp 2 Zr的[η 2 -Bu吨C⋮CB（C 6 F 5）2 ]（4a），Cp 2 ZrMe（C 6 F 5），有机硼烷Me 2 BC 6 F 5和甲烷气体是1a与3在甲苯中反应形成的最终产物在室温下溶解。通过变温NMR研究已经阐明了这种转化的化学计量机制。配合物4a和MeB（C 6 F 5）2（7）分别制备，并分别用作乙烯聚合催化剂和助催化剂。单独或在另外的1a的存在下，化合物4a对于乙烯聚合是惰性的。但是，Cp
• Organoborane-Modified Silica Supports for Olefin Polymerization:  Soluble Models for Metallocene Catalyst Deactivation
  作者：Robert A. Metcalfe、David I. Kreller、Jun Tian、Hoon Kim、Nicholas J. Taylor、John F. Corrigan、Scott Collins

  DOI：10.1021/om010284b

  日期：2002.4.1

  trifunctional organoborane 3, which was characterized by spectroscopic means and single-crystal X-ray crystallography. Compound 3 is an effective cocatalyst for ethylene polymerization in combination with Cp2ZrMe2 but only when these two compounds are combined in situ, in the presence of monomer, suggesting limited stability of the putative ion-pair derived from these compounds. Reaction of 3 with Cp2ZrMe2 in

  倍半硅氧烷的治疗1与3.3当量反应性有机硼烷的2 [（C 6 ˚F 5）2 BX; X ＝ H或Cl]提供了新颖的三官能的有机硼烷3，其通过光谱学手段和单晶X射线晶体学表征。化合物3是与Cp 2 ZrMe 2结合的用于乙烯聚合的有效助催化剂，但仅当这两种化合物在单体存在下就地结合时，表明衍生自这些化合物的推定离子对的稳定性有限。3与Cp 2 ZrMe 2的反应在室温下，甲苯溶液中的乙腈导致形成MeB（C 6 F 5）2-和Cp 2 Zr官能化的倍半硅氧烷5。在低温下通过NMR光谱监测此反应，表明存在的唯一离子对是[Cp 2 ZrMe] [Me 2 B（C 6 F 5）2 ]（4），这是由于Cp 2 ZrMe 2与副产物MeB（C 6 F 5）2。在这些条件下4的形成是可逆的，而5（来自3和Cp 2 ZrMe 2）不是；后一过程的发生速率超过了4独立分解形成Me 2 B（C 6 F 5）和Cp
• Nonchelated Alkene and Alkyne Complexes of d⁰ Zirconocene Pentafluorophenyl Cations
  作者：Edward J. Stoebenau、Richard F. Jordan

  DOI：10.1021/ja057524p

  日期：2006.7.1

  This paper describes the generation and properties of nonchelated d(0) zirconocene-aryl-alkene and alkyne adducts that are stabilized by the presence of beta-SiMe3 substituents on the substrates and the weak nucleophilicity of the -C6F5 ligand. The cationic complexes [(C5H4R)(2)Zr(C6F5)][B(C6F5)(4)] (4a: R) H, 4b: R) Me) were generated by methide abstraction from (C5H4R)(2)Zr(C6F5) Me by Ph3C+. NMR studies show that 4a,b contain an o-CF center dot center dot center dot Zr dative interaction and probably coordinate a PhCl molecule in PhCl solution. Addition of allyltrimethylsilane (ATMS) to 4a, b in C6D5Cl solution at low temperature produces an equilibrium mixture of (C5H4R)(2)Zr(C6F5)(H2CdCHCH2SiMe3)(+) (7a, b), 4a, b, and free ATMS. Similarly, addition of propargyltrimethylsilane (PTMS) to 4a produces an equilibrium mixture of Cp2Zr(C6F5)( HCtCCH(2)SiMe(3))(+) (8a), 4a, and free PTMS. The NMR data for 7a, b, and 8a are consistent with highly unsymmetrical substrate coordination and substantial polarization of the substrate multiple bond with significant positive charge buildup at C-int and negative charge buildup at C-term. PTMS binds to 4a more strongly than ATMS does. The ATMS adducts undergo nondissociative alkene face exchange ("alkene flipping"), i. e., exchange of the (C5H4R)(2)Zr(C6F5)(+) unit between the two alkene enantiofaces without decomplexation of the alkene, on the NMR time scale.
• Reaction of AlR₃ with [CPh₃][B(C₆F₅)₄]:  Facile Degradation of [B(C₆F₅)₄]^- by Transient “[AlR₂]⁺”
  作者：Bochmann、Mark J. Sarsfield

  DOI：10.1021/om980400j

  日期：1998.12.1
• Synthesis of the diborylated ferrocene 1,1'-bis-(bis-pentafluorophenylboryl)ferrocene and the X-ray structure of its trimethylphosphine adduct
  作者：Bryon E. Carpenter、Warren E. Piers、Robert McDonald

  DOI：10.1139/cjc-79-3-291

  日期：——

  The diborylated ferrocene compound 1,1'-Fc[B(C6F5)(2)](2) (2) was prepared via a transmetallation reaction involving 1,1'-Fc(HgCl)(2) and two equivalents of ClB(C6F5)(2). Although this reaction is very clean spectroscopically, isolated yields of 2 were never greater than 40% owing to the high solubility of the compound in non-donor solvents. Compound 2 is similar in its properties to the related monoborylated complex FcB(C6F5)(2) (1) reported previously, particularly the UV-vis spectrum, which exhibits an intense charge transfer absorption (lambda (max) = 233 nm, epsilon = 1.64 x 10(4)) assignable to an Fedz2/dx2-y2 --> B-p transition. However, 2, is significantly more Lewis acidic than 1, reacting with weak donors such as acetonitrile at room temperature, and effecting methide abstraction from Cp2ZrMe2 under mild conditions. Complex 2 also forms a bis(trimethylphosphine) adduct (3), which was structurally characterized via X-ray crystallography.