(perfluoro phenyl) titanium tri-isopropanolate | 53472-66-5

• 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: (perfluoro phenyl) titanium tri-isopropanolate
• 英文别名: [titanium(isopropoxide)3(pentafluorophenyl)]
• CAS: 53472-66-5
• 化学式: C₁₅H₂₁F₅O₃Ti
• 分子量: 392.202
• InChiKey: WTLQMKTVEREKCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  24.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  三异丙氧基氯化钛 、 五氟苯锂 以 乙醚 为溶剂， 以17%的产率得到(perfluoro phenyl) titanium tri-isopropanolate
  参考文献：
  名称：

  钛的一些σ-烷基和σ-芳基衍生物的制备及性能

  摘要：

  氯三异丙氧基钛与甲基锂或五氟苯基锂之间的反应分别产生了σ-甲基三异丙氧基钛和σ-五氟苯基三异丙氧基钛。这些有机钛化合物对水分非常敏感，并与苯溶液缔合。还描述了几种含有两个不同的σ键合有机取代基的钛茂衍生物的合成和性能。

  DOI：

  10.1016/s0022-328x(00)83764-x

文献信息

• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: F: PerFHalOrg.4, 1.3.3.8, page 33 - 59
  作者：

  DOI：——

  日期：——
• Ligand exchange and abstraction reactions involving titanium isopropoxide with tris(pentafluorophenyl)borane and -alane: ramifications for ring-opening polymerization of propylene oxide
  作者：Antonio Rodriguez-Delgado、Eugene Y.-X. Chen

  DOI：10.1016/j.ica.2004.05.015

  日期：2004.11

  In situ mixing of Ti((OPr)-Pr-i)(4) and B(C6F5)(3) generates a very efficient catalyst system for ring-opening polymerization (ROP) of propylene oxide (PO) with a turnover frequency (TOF) >1350/h, whereas the mixture of Ti((OPr)-Pr-i)(4) and Al(C6F5)(3) is inactive for the same polymerization. The inactivity of the Ti((OPr)-Pr-i)(4)/Al(C6F5)(3) mixture is due to the formation of the stable isopropoxy-bridged bimetallic species Ti((OPr)-Pr-i)(3)(mu-(OPr)-Pr-i)Al(C6F5)(3) (1), the structure of which has been confirmed by X-ray diffraction. The products of the Ti((OPr)-Pr-i)(4) + B(C6F5)(3) reaction, however, depend on the Ti((OPr)-Pr-i)(4):B(C6F5)(3) ratio. The 1: 1 ratio reaction in toluene at ambient temperature is rapid and produces the ligand exchange products: Ti((OPr)-Pr-i)(3)C6F5 and (PrOB)-Pr-i(C6F5)(2) (2), along with a small amount of ((PrO)-Pr-i)(2)BC6F5. The two resulting boranes are inseparable by recrystallization or vacuum distillation, and the formation of the undesired ((PrO)-Pr-i)(2)BC6F5 is either significantly enhanced upon heating the reaction in toluene to 80degreesC or nearly exclusive by carrying out the reaction in THF. By employing 1.2 equiv. of B(C6F5)(3) in the reaction with Ti((OPr)-Pr-i)(4), however, the formation of ((PrO)-Pr-i)(2)BC6F5 is suppressed, enabling the isolation of the new borane 2 in its pure state. The excess of B(C6F5)3 added to the reaction apparently slows down the exchange reaction by stabilizing the intermediate Ti((OPr)-Pr-i)(3)(mu-(OPr)-Pr-i)B(C6F5)(3) (4), as shown by the 1:2 Ti((OPr)-Pr-i)(4):B(C6F5)(3) reaction which initially forms the ligand abstraction product 4 followed by subsequent slow ligand exchange to give the final products Ti((OPr)-Pr-i)(3)C6F5 and 2. The studies of these individual reactions, in combination with control polymerization runs, reveal that the active species responsible for the catalytic activity of the Ti((OPr)-Pr-i)(4)/B(C6F5)(3) mixture is the isopropoxy borane 2. Thus, the isolated 2, in the absence or presence of a hydroxylic initiator, serves as a very effective catalyst for the ROP of PO, producing PPOs with M-n = 2000-3000, M-w/M-n = 1.30-1.43, and TOF > 1400/h. The MALDI-TOF NIS analyses of the PPOs formed show the linear PPO structures having the initiator and water molecules as end groups, demonstrating the control over the PPO structure. (C) 2004 Elsevier B.V. All rights reserved.