2-(2,7-ditert-butyl-9H-fluoren-9-yl)-N,N-dimethylethanamine | 1421618-55-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2-(2,7-ditert-butyl-9H-fluoren-9-yl)-N,N-dimethylethanamine
• CAS: 1421618-55-4
• 化学式: C₂₅H₃₅N
• 分子量: 349.56
• InChiKey: CSYSDDCONHPSLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [scandium(III)(chloride)3(tetrahydrofuran)3] 、 2-(2,7-ditert-butyl-9H-fluoren-9-yl)-N,N-dimethylethanamine 、 trimethylsilylmethyllithium 在 正丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 4.0h， 以0.18 g的产率得到(2,7-^tBu₂-9-CH₂CH₂NMe₂-fluorenyl)Sc(CH₂SiMe₃)₂
  参考文献：
  名称：

  Aluminum Effects in the Syndiospecific Copolymerization of Styrene with Ethylene by Cationic Fluorenyl Scandium Alkyl Catalysts

  摘要：

  A series of half-sandwich fluorenyl (Flu') scandium dialkyl complexes Flu'Sc(CH2SiMe3)(2)(THF)(n) (1, Flu' = C13H9, n = 1; 2, Flu' = 2,7-(Bu2C13H7)-Bu-t, n = 1; 3, Flu' = 9-SiMe3C13H8, n = 1; 4, Flu' = 2,7-Bu-t(2)-9-SiMe3C13H6, n = 1; 5, Flu' = 9-CH2CH2NMe2C13H6, n = 0; 6, Flu' = 2,7-Bu-t(2)-9-CH2CH2NMe2C13H6, n = 0) have been synthesized and structurally characterized. In comparison with the well-known cyclopentadienyl-ligated scandium catalyst system [(C5Me4SiMe3)Sc-(CH2SiMe3)(2)(THF)]/[Ph3C][B(C6F5)(4)], the analogous combinations of the fluorenyl-ligated, THF-containing complexes 1-4 with [Ph3C] [B(C6F5)(4)] show relatively low activities, albeit with similar syndioselectivities for styrene polymerization and styrene-ethylene copolymerization. However, on treatment with 15 equiv of (AlBu3)-Bu-t, the 1-4/[Ph3C][B(C6F5)(4)] combinations show a dramatic increase in catalytic activity without changes in the stereoselectivity. In contrast, the combinations of complexes 5 and 6, which have an amino group attached to the fluorenyl ring and intramolecularly bonded to the metal center, exhibit very low activity, no matter whether or not All3u3 is present, affording syndiotactic polystyrenes with broad molecular weight distributions. The DFT calculations of the activation mechanism by using the representative catalysts suggest that Arl3u3 can capture the THF molecule from the catalyst precursors 1-4 at first,and then the new, THF-free cationic half-sandwich scandium active species [Flu'Sc(CH2SiMe3)][B(C6F5)(4)] with less steric hindrance around the metal center is generated in the presence of an activator such as [Ph3C][B(C6F5)(4)]. The DFT calculations on the syndioselectivity of styrene (co)polymerization catalyzed by [Flu'Sc(CH2SiMe3)][B(C6F5)(4)] have also been carried out, thus shedding new light on the mechanistic aspects of the (co)polymerization processes.

  DOI：

  10.1021/om3011036