3,6-di-tert-butyl-9-{(4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)(diphenyl)methyl}-9H-fluorene | 1013910-97-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3,6-di-tert-butyl-9-{(4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)(diphenyl)methyl}-9H-fluorene
• 英文别名: 3,6-ditert-butyl-9-[(4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)-diphenylmethyl]-9H-fluorene
• CAS: 1013910-97-8
• 化学式: C₄₄H₅₀
• 分子量: 578.881
• InChiKey: HMSLXWBOTGQIAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.4
• 重原子数：
  44
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  6,6'-diphenyl-3-tert-butyl-5-methylfulvene 以2%的产率得到3,6-di-tert-butyl-9-{(4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)(diphenyl)methyl}-9H-fluorene
  参考文献：
  名称：

  New C₁-Symmetric Ph₂C-Bridged Multisubstituted ansa-Zirconocenes for Highly Isospecific Propylene Polymerization: Synthetic Approach via Activated Fulvenes

  摘要：

  The synthesis of multisubstituted diphenylmethylene-bridged fluorenyl-cyclopentadienyl proligands Ph2C(3,6-tBu(2)FluH)(3-R-1-5-(RC5H3)-C-2) (Flu = fluorenyl; R-1 = tert-butyl, R-2 = H (2a); R-1 = tert-butyl, R-2 = Me (2b); R-1 = cumyl, R-2 = Me (2c)) was developed using a nucleophilic addition protocol based on regular and activated fulvenes. Two highly congested proligands (2b,c) were prepared in a two-step procedure, starting first by addition of [3,6-tBu(2)Flu]Li-+(-) onto 6,6'-bis(p-chlorophenyl)fulvenes, followed by a Pd-catalyzed reductive dechlorination. The X-ray crystal structures of 2a and 2b center dot CH2Cl2 were determined. These revealed a preorganized sandwich-like positioning of the fluorenyl and cyclopentadienyl plane fragments, similar to that observed in the metallocenes. The corresponding dichlorozirconium complexes {Ph2C(3,6-tBu(2)Flu)(3-R-1-5-R-2-C5H2)}ZrCl2 (R-1 = tert-butyl, R-2 = H (3a); R-1 = tert-butyl, R-2 = Me (3b); R-1 = cumyl, R-2 = Me (3c)) were prepared by salt metathesis and characterized by elemental analysis, NMR spectroscopy, and X-ray crystallography (for 3a,c). These C-1-symmetric zirconocenes exist as racemic mixtures of two enantiomers, arising from planar chirality at the Cp ring. When activated with MAO, 3a,b showed high activity in the polymerization of propylene (5020 and 3580 kg of iPP mol(-1) h(-1), respectively; toluene solution, 60 degrees C), affording highly isotactic ([m(4)] 94.0%) polymers with molecular weights in the range M-w = 30 000-175 000, which are similar to those obtained with the corresponding CMe2-bridged catalysts. No activity was observed with the 3c/MAO system, which was proposed to be due to a deactivation involving a cumyl phenyl ring. This was supported by OFT computations on the cationic species [{Ph2C(3,6-tBu(2)Flu)(3-cumyl-5-Me-C5H2)}ZrMe](+) which revealed facile coordination of the phenyl ring to the metal center, followed by C-H(phenyl) activation at the ortho position with concomitant elimination of methane; propylene insertion into the resulting ortho-metalated species was found to be thermodynamically unfavorable.

  DOI：

  10.1021/om100289y

文献信息

• WO2008/37608
  申请人：——

  公开号：——

  公开（公告）日：——
• New <i>C</i>₁-Symmetric Ph₂C-Bridged Multisubstituted <i>ansa</i>-Zirconocenes for Highly Isospecific Propylene Polymerization: Synthetic Approach via Activated Fulvenes
  作者：Evgeny Kirillov、Nicolas Marquet、Abbas Razavi、Vincenzo Belia、Frank Hampel、Thierry Roisnel、John A. Gladysz、Jean-François Carpentier

  DOI：10.1021/om100289y

  日期：2010.11.8

  The synthesis of multisubstituted diphenylmethylene-bridged fluorenyl-cyclopentadienyl proligands Ph2C(3,6-tBu(2)FluH)(3-R-1-5-(RC5H3)-C-2) (Flu = fluorenyl; R-1 = tert-butyl, R-2 = H (2a); R-1 = tert-butyl, R-2 = Me (2b); R-1 = cumyl, R-2 = Me (2c)) was developed using a nucleophilic addition protocol based on regular and activated fulvenes. Two highly congested proligands (2b,c) were prepared in a two-step procedure, starting first by addition of [3,6-tBu(2)Flu]Li-+(-) onto 6,6'-bis(p-chlorophenyl)fulvenes, followed by a Pd-catalyzed reductive dechlorination. The X-ray crystal structures of 2a and 2b center dot CH2Cl2 were determined. These revealed a preorganized sandwich-like positioning of the fluorenyl and cyclopentadienyl plane fragments, similar to that observed in the metallocenes. The corresponding dichlorozirconium complexes Ph2C(3,6-tBu(2)Flu)(3-R-1-5-R-2-C5H2)}ZrCl2 (R-1 = tert-butyl, R-2 = H (3a); R-1 = tert-butyl, R-2 = Me (3b); R-1 = cumyl, R-2 = Me (3c)) were prepared by salt metathesis and characterized by elemental analysis, NMR spectroscopy, and X-ray crystallography (for 3a,c). These C-1-symmetric zirconocenes exist as racemic mixtures of two enantiomers, arising from planar chirality at the Cp ring. When activated with MAO, 3a,b showed high activity in the polymerization of propylene (5020 and 3580 kg of iPP mol(-1) h(-1), respectively; toluene solution, 60 degrees C), affording highly isotactic ([m(4)] 94.0%) polymers with molecular weights in the range M-w = 30 000-175 000, which are similar to those obtained with the corresponding CMe2-bridged catalysts. No activity was observed with the 3c/MAO system, which was proposed to be due to a deactivation involving a cumyl phenyl ring. This was supported by OFT computations on the cationic species [Ph2C(3,6-tBu(2)Flu)(3-cumyl-5-Me-C5H2)}ZrMe](+) which revealed facile coordination of the phenyl ring to the metal center, followed by C-H(phenyl) activation at the ortho position with concomitant elimination of methane; propylene insertion into the resulting ortho-metalated species was found to be thermodynamically unfavorable.