AlⁱBu₃(THF) | 4830-00-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: AlⁱBu₃(THF)
• 英文别名: aluminum(isobutyl)3(THF)
• CAS: 4830-00-6
• 化学式: C₁₆H₃₅AlO
• 分子量: 270.435
• InChiKey: GPOPIOGIXNUVER-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：
  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

• 作为产物：
  描述：

  (9-SiMe₃-fluorenyl)Sc(CH₂SiMe₃)₂(THF) 、 三异丁基铝 以 氘代苯 、 甲苯 为溶剂， 生成 AlⁱBu₃(THF)
  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

文献信息

• Olefin Polymerization Catalyst Derived by Activation of a Neutral Monoalkyl Titanium Complex with an Aminopyrrole Ligand Using Triisobutylaluminum and Trityl Borate
  作者：Takahiro Yasumoto、Tsuneaki Yamagata、Kazushi Mashima

  DOI：10.1246/cl.2007.1030

  日期：2007.8.5

  A neutral monocyclopentadienyl titanium monobenzyl complex 3a bearing an aminopyrrole ligand can be activated by treating with Al(iBu)3 and [Ph3C][B(C6F5)4] to became a catalyst for olefin polymeri...

  带有氨基吡咯配体的中性单环戊二烯基钛单苄基配合物 3a 可以通过用 Al(iBu)3 和 [Ph3C][B(C6F5)4] 处理而活化，成为烯烃聚合的催化剂。
• Drei- oder Vierfach-Koordination des Aluminiums in Alkylaluminiumphenoxiden und deren Unterscheidung durch 27Al-NMR-Spektroskopie
  作者：Reinhard Benn、Edo Janssen、Herbert Lehmkuhl、Anna Rufińska、Klaus Angermund、Peter Betz、Richard Goddard、Carl Krüger

  DOI：10.1016/0022-328x(91)86004-a

  日期：1991.7

  The Al-27 NMR spectra for a series of aryloxyaluminium compounds [R(n)Al(OAr)3-n]m (R = methyl, isobutyl; n = 0-2; m = 1, 2, 3) with various alkyl substituents in the 2 and 6 positions of the phenoxy rings have been measured. The delta-(Al-27) resonances give an indication of the number of aryloxy ligands and the coordination number of each Al atom. Monomeric R2AlOAr compounds have delta-(Al-27) resonances around 190 ppm whereas dimeric analogues give signals at 167 ppm. The Al-27 NMR resonances for monomeric RAl(OAr)2 are found at ca. 100 ppm while those for [Al(OAr)3]2, where the aluminium atoms are solely bonded to aryloxyl groups, lie at ca. 50 ppm. Characteristic shifts of the resonances were also observed for complexes of these compounds with THF, whereby it was found that the resulting change DELTA-delta-(Al-27) decreases with increasing number of aryloxy ligands. The crystal structures of three selected compounds, 3, 8 and 11, were determined by X-ray crystallography.