tris(2,6-diisopropylphenolato)titanium(IV) chloride | 151041-52-0

• 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: tris(2,6-diisopropylphenolato)titanium(IV) chloride
• 英文别名: tris(2,6-diisopropylphenolato)titanium chloride；tris(2,6-diisopropylphenoxo)titanium chloride；tris(2,6-diisopropylphenoxy)titanium chloride；[TiCl(2,6-di-iso-propylphenolate)3]
• CAS: 151041-52-0
• 化学式: C₃₆H₅₁ClO₃Ti
• 分子量: 615.132
• InChiKey: GPWMJCUIKXXPIU-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  12.02
• 重原子数：
  41.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-lithio-2,4,6-trimethylborazine diethyl ether adduct 、 tris(2,6-diisopropylphenolato)titanium(IV) chloride 以 乙醚 为溶剂， 以80%的产率得到tris(2,6-diisopropyl-phenoxo)-N-(2,4,6-trimethylborazinyl)titanium
  参考文献：
  名称：

  N-(2,4,6-Trimethylborazinyl)-substituted Boron, Aluminum and Titanium Compounds

  摘要：

  N-锂硼氮杂环戊烷LiH₂N₃B₃Me₃，1，不仅与有机硼卤化物反应生成相应的硼氮杂环有机硼烷，还发生Me/卤素交换反应。从1和(Me₂N)₂BCl得到了(Me₂N)₂B-H₂N₃B₃Me₃。通过用1处理Cl(Me₂N)B-B(NMe₂)Cl得到了一个新的十元环B₆N4>环系统5。硼氮硼氮杂环6-8可以通过1和B-单卤代硼氮杂环制备。只有Al(III)和Ti(IV)的单核单卤化物才能合成2,4,6-三甲基硼氮杂环铝和钛化合物。2,4,6-三甲基硼氮杂环-双(哌啶基)铝9和三(2,6-二异丙基苯氧基)-2,4,6-三甲基硼氮杂环钛10通过X射线结构分析进行了表征。

  通过B和N取代引起的硼氮杂环畸变进行了讨论。对于N取代的硼氮杂环YH₂N₃B₃Me₃，YNB₂单元的B-N键被延长，例如对于Y = PBr₂或(RO)₃Ti，而N锂化导致这些B-N键的缩短。这些键长的变化也反映在B1-N2和B3-N3键长的变化上，在电子吸引基团存在时变短，但在锂取代的情况下变长。此外，键角B1-N2-B2和B2-N3-B3受到影响，最多增加128°。

  DOI：

  10.1515/znb-2008-0105
• 作为产物：
  描述：

  丙泊酚 、 四氯化钛 以 苯 为溶剂， 以94%的产率得到tris(2,6-diisopropylphenolato)titanium(IV) chloride
  参考文献：
  名称：

  三（2,6-二异丙基苯酚）钛（IV）二氢二有机基硼酸盐：合成和结构

  摘要：

  三（2,6-二异丙基苯酚）氯化钛（IV）与碱金属二氢二有机基硼酸盐 M（H2BR2）（M = Li，K；R = Me，C6H11，CMe3；BR2 = BC5H10，BC8H14）的反应导致了相应的二氢二有机硼酸钛。然而，在几乎所有情况下，也会产生副产物，例如（2,6-二异丙基苯酚）二有机基硼烷、三有机基硼烷、二有机基硼烷、乙硼烷和四（2,6-二异丙基苯酚）钛 (IV)。(2,6-iPr2C6H3O)3Ti(H2BR2) 化合物也是甲基三（2,6-二异丙基苯酚）钛与儿茶酚硼烷相互作用的产物。除了生成三（2,6-二异丙基苯酚）儿茶酚硼钛（IV）外，还生成了 B-甲基儿茶酚硼烷。二氢-9-环辛基硼酸钾与 2,6-双（2，2-二叔丁基-2-羟乙基）吡啶二氯化钛（LTiCl2）生成复合物LTi（H2BC8H14）2。与 (2,6-iPr2C6H3O)3TiH2BC8H14 和相应的二氢化双（环己基）硼酸钛相比，该化合物没有表现出激动的

  DOI：

  10.1002/ejic.201001108

文献信息

• Unusual Formation of Two New Titanium(IV) Tetraphenolates
  作者：Jörg Knizek、Heinrich Nöth

  DOI：10.1515/znb-2011-0110

  日期：2011.1.1

  When the product of the reaction of 2,6-di-tert.-butylphenol with TiCl₄ in a 3:1 ratio is treated with Na[HBEt₃], the isolated product is not (2,6-tert.-Bu2C6H3O)3Ti(HBEt3) but the isomerized ester (2,4-tert.-Bu₂C₆H₃O)₄Ti with molecular S₄ symmetry. This rearrangement of the R substituents does not occur upon reacting 2,6-diisopropylphenol with TiCl₄ and Na[HBEt₃]. An unexpected result is also observed for the product of the reaction of tris(2,6-diisopropylphenolato)titanium(IV) chloride with lithium bis(pentafluorophenolato)dihydridoborate. The isolated product proved to be dimeric tris(pentafluorophenolato)(2,6-diisopropylphenolato)titanium(IV) with two bridging pentafluorophenolato groups generating pentacoordinated Ti atoms

  当2,6-二叔丁基苯酚和TiCl4以3:1的比例反应生成物质，经过Na[HBEt3]处理后，所得到的分离产物不是(2,6-叔丁基2C6H3O)3Ti(HBEt3)，而是异构化酯(2,4-叔丁基2C6H3O)4Ti，具有分子S4对称性。在TiCl4和Na[HBEt3]反应时，2,6-二异丙基苯酚的R取代基没有发生这种重排。对于三(2,6-二异丙基苯酚氧)四钛(IV)氯和锂双(五氟苯氧基)氢硼酸盐反应产物的意外结果也被观察到。分离出的产物被证明是二聚体三(五氟苯氧基) (2,6-二异丙基苯酚氧)四钛(IV)，具有两个桥联五氟苯氧基团，生成五配位的钛原子。
• Shah, A.; Singh, A.; Mehrotra, R. C., Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1993, vol. 32, # 7, p. 632 - 635
  作者：Shah, A.、Singh, A.、Mehrotra, R. C.

  DOI：——

  日期：——
• Molecular engineering of coordination pockets in chloro-tris-phenoxo complexes of titanium(IV)
  作者：Alastair J. Nielson、Chaohong Shen、Joyce M. Waters

  DOI：10.1016/j.poly.2005.12.027

  日期：2006.7

  The chloro-tris-phenoxo complexes [TiCl(OAr)(3)] (OAr = OC6H4CMe-(3)-4 (1). OC6H2Me3-2A (2). OC6H2Me3-2,4,6 (4), OC6H3(CHMe2)(2)-2,6 (5), OC6H3(CMe3)(2)-2,4 (6) and OC6H4Ph-2 (8) are prepared by heating 3 equivalents of the phenol and [TiCl4] in toluene. X-ray crystal structure determinations show that 2 is a phenoxy-bridged dimer with the ortho-methyl groups making the beginning of a pocket about the terminal chloro ligand and 6 is a tetrahedral monomer in which the pocket is more well developed by the ortho-tert-butyl groups. Both 2 and 6 react with dmbipy to give [TiCl(OAr)(3)(dmbipy)] [OAr = OC6H3Me2-2,4 (3) and OC6H3(CMe3)2-2,4 (7)] in which the original pocket is destroyed. Reaction of TiCl4 with 3 equivalents of LiOC6H4Ph-2 in diethyl ether gives [TiCl(OC6H4Ph-2)(3)(diethyl ether)] (9) for which an X-ray crystal structure determination shows a trigonal bipyramidal coordination geometry with the diethyl ether lying trans to the chloro ligand. The three phenoxide ligands make up the equatorial plane which takes the 2-phenyl substituent on each phenoxo ligand away from the chloro ligand resulting in a partially collapsed cavity. The tied-back analogues of 2 and 6, [TiClOC6H2Me2-2,4-CH2-6)(3)N)] (11) and [TiCl(OC6H2(CMe3)(2)-2,4-CH2-6}(3)N)] (.) diethyl ether (12), are prepared by adding (HOArCH2)(3)N [Ar = C6HMe2-2,4 and C6H2(CMe3)(2) 2.4] to [TiCl(OCHMe2)(3)] in diethyl ether. An X-ray crystal structure of 12 showed a trigonal bipyramidal structure with a coordination environment about the terminal chloro ligand similar to that found in 6. Complex 12 reacts with pyridine to form the 6-coordinate complex [TiClOC6H2(CMe3)(2)-2,4-CH2-6)(3)N)(py)] (13). (c) 2006 Elsevier Ltd. All rights reserved.
• Nöth, Heinrich; Schmidt, Martin, Organometallics, 1995, vol. 14, # 10, p. 4601 - 4610
  作者：Nöth, Heinrich、Schmidt, Martin

  DOI：——

  日期：——