dimethylsilyl-(tertiarybutylamino)-(3,6-ditertiarybutylfluorene) | 329722-48-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: dimethylsilyl-(tertiarybutylamino)-(3,6-ditertiarybutylfluorene)
• 英文别名: dimethylsilyl-(tert-butylamino)-(3,3-di-tert-butylfluorene)；(3,6-(tert-butyl)2C13H7)Si(methyl)2NH(tert-butyl)；N-[(3,6-ditert-butyl-9H-fluoren-9-yl)-dimethylsilyl]-2-methylpropan-2-amine
• CAS: 329722-48-7
• 化学式: C₂₇H₄₁NSi
• 分子量: 407.715
• InChiKey: XAIFFDLCUHCQBQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.53
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  四氯化钛 、 dimethylsilyl-(tertiarybutylamino)-(3,6-ditertiarybutylfluorene) 在 methyl lithium 作用下， 以 正戊烷 为溶剂， 生成 eta.1,η5-tert-butyl-(3,6-bis-tert-butylfluorenyl-dimethylsilyl)amidodichlorotitanium
  参考文献：
  名称：

  Preparation and crystal structures of the complexes (η5-C5H3TMS–CMe2–η5-C13H8)MCl2 and [3,6-ditButC13H6–SiMe2–NtBu]MCl2 (M=Hf, Zr or Ti): mechanistic aspects of the catalytic formation of a isotactic–syndiotactic stereoblock-type polypropylene

  摘要：

  The reaction of MCl4, (M = Zr or Hf) with the dilithium salt of 2-(3-trimethylsilyl-cydopentadienyl)-2-florenylpropane in pentane leads to the formation of the complexes (eta (5)-C5H3TMS-CMe2-eta (5)-C13H8)MCl2 (M = Zr or Hf; TMS = trimethylsilyl). The X-ray diffraction data show that both the fluorenyl and cyclopentadienyl groups are 175 bonded to the transition metal in these complexes in the solid phase. The polymerization data and the polymer microstructure, however, clearly indicate that at least after the activation with MAO the active species formed with these molecules show very dynamic bonding behavior and their substituted cyclopentadienyl group changes its hapticity rapidly and frequently during the course of the polymerization. (C) 2001 Published by Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00863-9
• 作为产物：
  描述：

  3,6-二叔丁基黄酮 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 3.0h， 生成 dimethylsilyl-(tertiarybutylamino)-(3,6-ditertiarybutylfluorene)
  参考文献：
  名称：

  的取代基效应叔对芴基配体丁基组在丙烯间规活性聚合与一个NSA -Fluorenylamidodimethyltitanium情结

  摘要：

  [吨-BuNSiMe 2（2,7-吨-Bu 2流感）]时间2和[吨-BuNSiMe 2（3,6-吨-Bu 2时间感）] 2的合成和表征通过元素分析，1 1 H NMR ，以及单晶X射线分析。这些配合物用于在0和25°C下使用干燥的改性甲基铝氧烷（dMMAO）作为助催化剂进行丙烯聚合。介绍叔叔芴基配体的-丁基取代基将活性提高了3倍以上，而与取代基的位置无关。后聚合证明，两个催化体系均在0和25°C下以活性方式进行了丙烯聚合。在保持聚合物链数不变的情况下，传播速率相对于Al / Ti比从100-400线性增加，这直接表明较大量的dMMAO可以提高传播速率。引入的叔丁基取代基也改善了syndiospecificity：3,6-位置比2,7位更有效，并[吨-BuNSiMe 2（3,6-吨-Bu 2流感）]时间2 得到间规三单元组为0.93，熔点为142℃的活性聚丙烯。

  DOI：

  10.1021/ma050898i

文献信息

• “Constrained Geometry” Group 3 Metal Complexes of the Fluorenyl-Based Ligands [(3,6-^tBu₂Flu)SiR₂N^tBu]:  Synthesis, Structural Characterization, and Polymerization Activity
  作者：Evgueni Kirillov、Loic Toupet、Christian W. Lehmann、Abbas Razavi、Jean-François Carpentier

  DOI：10.1021/om0304210

  日期：2003.10.1

  hydrido complex “[(3,6-tBu2Flu)SiMe2NtBu)YH(THF)]n” (3). Deprotonation of 1a with 1 and 2 equiv of nBuLi gave [(3,6-tBu2C13H6)SiMe2NHtBu]Li (5) and [(3,6-tBu2C13H6)SiMe2NtBu]Li2 (4), respectively, both of which were characterized crystallographically. Salt elimination reactions between LnCl3(THF)n precursors (Ln = Y, La, Nd) and 1 equiv of 4 gave mixtures of complexes, from which ionic complexes that

  Y（CH 2 SiMe 3）3（THF）2与双旋配体[（3,6- t Bu 2 C 13 H 7）SiR 2 NH t Bu]之间的烷烃消除（R = Me，1a ; R = Ph，图1b），得到[η 3：η 1 - （（3,6-吨卜2 ç 13 ħ 6）SIR 2 ñ吨卜）Y（CH 2森达3）（THF）2 ]（R = Me中，图2a ; R = Ph，2b）。2a在甲苯溶液中是热稳定的，并显示出与THF解离有关的动力学行为，而2b是热不稳定的。的反应图2a用H 2或PhSiH 3导致了推定的氢基复合物“[（3,6-吨卜2流感）森达2 Ñ吨丁基）YH（THF）] ñ ”（3）。用1和2当量的n BuLi对1a进行质子化，得到[（3,6- t Bu 2 C 13 H 6）SiMe 2 NH t Bu] Li（5）和[（3,6- t Bu 2 C 13 H 6）SiMe 2 N t Bu] Li
• Substituent Effects of <i>tert</i>-Butyl Groups on Fluorenyl Ligand in Syndiospecific Living Polymerization of Propylene with <i>a</i><i>nsa</i>-Fluorenylamidodimethyltitanium Complex
  作者：Zhengguo Cai、Tomiki Ikeda、Munetaka Akita、Takeshi Shiono

  DOI：10.1021/ma050898i

  日期：2005.10.1

  applied for propylene polymerization using dried modified methyaluminoxane (dMMAO) as a cocatalyst at 0 and 25 °C. The introduction of tert-butyl substituents to the fluorenyl ligand improved the activity more than 3 times regardless of the position of the substituents. The postpolymerization testified that both catalytic systems conducted the propylene polymerization in a living manner at both 0 and

  [吨-BuNSiMe 2（2,7-吨-Bu 2流感）]时间2和[吨-BuNSiMe 2（3,6-吨-Bu 2时间感）] 2的合成和表征通过元素分析，1 1 H NMR ，以及单晶X射线分析。这些配合物用于在0和25°C下使用干燥的改性甲基铝氧烷（dMMAO）作为助催化剂进行丙烯聚合。介绍叔叔芴基配体的-丁基取代基将活性提高了3倍以上，而与取代基的位置无关。后聚合证明，两个催化体系均在0和25°C下以活性方式进行了丙烯聚合。在保持聚合物链数不变的情况下，传播速率相对于Al / Ti比从100-400线性增加，这直接表明较大量的dMMAO可以提高传播速率。引入的叔丁基取代基也改善了syndiospecificity：3,6-位置比2,7位更有效，并[吨-BuNSiMe 2（3,6-吨-Bu 2流感）]时间2 得到间规三单元组为0.93，熔点为142℃的活性聚丙烯。
• Preparation and crystal structures of the complexes (η5-C5H3TMS–CMe2–η5-C13H8)MCl2 and [3,6-ditButC13H6–SiMe2–NtBu]MCl2 (M=Hf, Zr or Ti): mechanistic aspects of the catalytic formation of a isotactic–syndiotactic stereoblock-type polypropylene
  作者：Abbas Razavi、Ulf Thewalt

  DOI：10.1016/s0022-328x(00)00863-9

  日期：2001.3

  The reaction of MCl4, (M = Zr or Hf) with the dilithium salt of 2-(3-trimethylsilyl-cydopentadienyl)-2-florenylpropane in pentane leads to the formation of the complexes (eta (5)-C5H3TMS-CMe2-eta (5)-C13H8)MCl2 (M = Zr or Hf; TMS = trimethylsilyl). The X-ray diffraction data show that both the fluorenyl and cyclopentadienyl groups are 175 bonded to the transition metal in these complexes in the solid phase. The polymerization data and the polymer microstructure, however, clearly indicate that at least after the activation with MAO the active species formed with these molecules show very dynamic bonding behavior and their substituted cyclopentadienyl group changes its hapticity rapidly and frequently during the course of the polymerization. (C) 2001 Published by Elsevier Science B.V. All rights reserved.