dichlorobis[η(5)-(pentafluorophenyl)cyclopentadienyl]zirconium(IV) | 184481-08-1

• 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: dichlorobis[η(5)-(pentafluorophenyl)cyclopentadienyl]zirconium(IV)
• 英文别名: 1-cyclopenta-2,4-dien-1-yl-2,3,4,5,6-pentafluorobenzene;dichlorozirconium(2+)
• CAS: 184481-08-1
• 化学式: C₂₂H₈Cl₂F₁₀Zr
• 分子量: 624.42
• InChiKey: JZQBXWKRRBJZKE-UHFFFAOYSA-L

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：

  dichlorobis[η(5)-(pentafluorophenyl)cyclopentadienyl]zirconium(IV) 、 甲基锂 以 甲苯 为溶剂， 以82%的产率得到1,1'-bis(pentafluorophenyl)zirconocene dimethide
  参考文献：
  名称：

  Analysis of Metallocene−Methylalumoxane Methide Transfer Processes in Solution Using a ¹⁹F NMR Spectroscopic Probe

  摘要：

  The metallocenes (C6F5C5H4)CpZrMe2 (1, Cp = C5H5) and (C6F5C5H4)(2)MMe2 (2a, M = Zr; 2b, M = Hf) were treated with B(C6F5)(3) and, separately, with commercial methylalumoxane (MAO, depleted of excess Me3Al). The ensuing methide transfer reactions were followed by F-19 NMR. Spectra of the "activated" species obtained using MAO and excess B(C6F5)3 were strikingly similar, suggesting that similar "cation-like" species are formed using either organo-Lewis acid, and the MAO-activated species were tentatively formulated as (C6F5C5H4)CpZrMe+ Me[AlMeO](n)(-) and as (C6F5C5H4)(2)MMe+ Me[AlMeO](n)(-) (M = Zr, Hf). The relative amount of L2MMe2 and [L2MMe](+) species observed in solution was measured as a function of [MAO] and as a function of [M] at constant [MAO]. Results are interpreted in terms of a canonical model in which MAO contains relatively few highly active Lewis acidic sites.

  DOI：

  10.1021/om030171n
• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 sodium (pentafluorophenyl)cyclopentadienide 以 甲苯 为溶剂， 以73%的产率得到dichlorobis[η(5)-(pentafluorophenyl)cyclopentadienyl]zirconium(IV)
  参考文献：
  名称：

  Synthesis of Pentafluorophenyl-Substituted Cyclopentadienes and Their Use as Transition-Metal Ligands

  摘要：

  The reaction of NaC5H5 (NaCp) and hexafluorobenzene (1:1 ratio) in THF at 25 degrees C for 15 h afforded, after hydrolysis, a mixture of regioisomeric (pentafluorophenyl)cyclopentadienes. This mixture was isolated as a monoisomeric dimer of 1-(pentafluorophenyl)cyclopentadiene. The structure of the dimer was determined crystallographically. Flash vacuum thermolytic cracking of the dimer at 200 degrees C regenerated (pentafluorophenyl)cyclopentadiene as a mixture of regioisomers. In contrast, the reaction of NaCp, NaH, and C6F6 (1:2:5 ratio) in THF at reflux for 3 d affords, after hydrolysis, 1,4-bis(pentafluorophenyl)cyclopentadiene which does not dimerize. Either the mono- or the disubsubstituted diene reacts with NaH in THF;to afford the corresponding stable substituted sodium cyclopentadienides in high yields. Sodium (pentafluorophenyl)cyclopentadienide, (C6F5)C5H4Na, reacted with FeBr2, Re(CO)(5)Br, and ZrCl4(THF)(2), to afford the transition metal complexes (eta(5)-C5H4C6F5)(2)Fe, (eta(5)-C6H4C6F5)Re(CO)(3), and (eta(5)-C5H4C6F5)(2)ZrCl2. Sodium 1,3-bis(pentafluorophenyl)cyclopentadienide reacted with FeBr2 and Re(CO)(5)Br to give the corresponding complexes [eta(5)-1,3-C5H3(C6F5)(2)]Fe-2 and [eta(5)-1,3-C5H3(C6F5)(2)]Re(CO)(3). Infrared spectroscopic analysis of the tricarbonylrhenium(I) complexes and cyclic voltammetric analysis of the substituted ferrocenes quantified the strong electron-withdrawing effects of the pentafluorophenyl substituents.

  DOI：

  10.1021/om9608216

文献信息

• Selective Halodemethylation Reactions of Metallocene Dimethyls with Triphenylmethyl Chloride and Benzyl Bromide
  作者：Eric J. Hawrelak、Paul A. Deck

  DOI：10.1021/om0305014

  日期：2004.1.1

  NMR-scale reactions of several group 4 metallocene dimethyls with either trityl chloride or benzyl bromide gave the corresponding L2M(Me)X complexes selectively. Five reactions, including syntheses of Cp2Zr(Me)Cl and Ind2Zr(Me)Cl, were conducted on a preparative scale to afford useful isolated yields of L2M(Me)Cl complexes.

  几种4号茂金属二甲基与三苯甲基氯或苄基溴的NMR规模反应选择性地产生了相应的L 2 M（Me）X络合物。在制备规模上进行了五个反应，包括Cp 2 Zr（Me）Cl和Ind 2 Zr（Me）Cl的合成，以提供有用的L 2 M（Me）Cl复合物的分离产率。