4,5,6,7-tetrahydroindenyltrichlorotitanium | 32715-00-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 4,5,6,7-tetrahydroindenyltrichlorotitanium
• 英文别名: 4,5,6,7-tetrahydro-1H-inden-1-ide;trichlorotitanium(1+)
• CAS: 32715-00-7
• 化学式: C₉H₁₁Cl₃Ti
• 分子量: 273.425
• InChiKey: SQDVXBMZYMBAFU-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -6.71
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,5,6,7-tetrahydroindenyltrichlorotitanium 、 甲基氯化镁 以 四氢呋喃 、 乙醚 为溶剂， 以98%的产率得到(4,5,6,7-tetrahydroindenyl)TiMe3
  参考文献：
  名称：

  Preparation and X-ray Structures of Alkyl−Titanium(IV) Complexes Stabilized by Indenyl Ligands with a Pendant Ether or Amine Substituent and Their Use in the Catalytic Hydroamination of Alkynes

  摘要：

  Complexes Ind(X)TiCl(3) (1, 2) react with 1.0, 2.0, and 3.0 equiv of MeMgCl to give Ind(X)TiMeCl(2) (3, 4), Ind(X)TiMe(2)Cl (5, 6), and Ind(X)TiMe(3) (7, 8), respectively (X = CH2CH2OMe (1, 3, 5, 7), CH2CH2NMe2 (2, 4, 6, 8). Complexes 3, 6, and 8 have been characterized by X-ray diffraction analysis. The structures prove that in the solid state the pendant substituents of the indenyl ligands are coordinated to the metal center (d(Ti-O) = 2.296(3) A (3); d(Ti-N) = 2.4006(19) (6), 2.4214(17) A (8) disposed transoid to a methyl ligand. In solution the pendant donor groups are involved in coordination-dissociation equilibria (Delta H degrees = 4.2 +/- 0.6 kcal mol(-1) and Delta S degrees = 15.5 +/- 3 eu for 3 ; Delta H degrees = 3.4 +/- 0.2 kcal mol(-1) and Delta S degrees = 11.6 +/- 0.3 eu for 4; Delta H degrees = 3.5 +/- 1.1 kcal mol(-1) and Delta S degrees = 15.2 +/- 4.4 eu for 5; Delta H degrees = 4.3 +/- 1.3 kcal mol(-1) and Delta S degrees = 16.0 +/- 2.8 eu for 6; Delta H degrees = 2.2 +/- 0.5 kcal mol(-1) and Delta S degrees = 11.0 +/- 2.2 eu for 7; Delta H degrees = 4.9 +/- 0.5 kcal mol(-1) and Delta S degrees = 20.8 +/- 2.2 eu for 8). Complexes 7, 8, IndTiMe(3) (9), and H(4)IndTiMe(3) (10; H(4)Ind = 4,5,6,7-tetrahydroindenyl) are efficient catalyst precursors for the regioselective hydroamination of 1-octyne, phenylacetylene, and 1-phenylpropyne with aromatic (2,6-dimethylaniline and 2,6-diisopropylaniline) and aliphatic (tert-butylamine, dodecylamine, and cyclohexylamine) amines. The reactions give imine or imine-enamine mixtures, which are reduced to the corresponding secondary amines. The Markovnikov or anti-Markovnikov nature of the obtained products depends on the aliphatic or aromatic character of both the alkyne and the amine. Markovnikov products with regioselectivities of 100% are formed from the reactions between 1-octyne and aromatic amines, while anti-Markovnikov derivatives with regioselectivities of 100% are obtained from the reactions of aromatic alkynes with all the studied amines and from the reactions of 1-octyne with tert-butylamine and dodecylamine. The reactions of 1-octyne with cyclohexylamine give mixtures of both types of products. A comparative study between the catalytic efficiencies of 7-10 and those of their cyclopentadienyl counterparts is also included (Table 4).

  DOI：

  10.1021/om060909b
• 作为产物：
  描述：

  三氯(吲哚基)钛 、 氢气 在 platinum(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到4,5,6,7-tetrahydroindenyltrichlorotitanium
  参考文献：
  名称：

  Alkyl-substituted indenyl titanium precursors for syndiospecific ziegler-natta polymerization of styrene

  摘要：

  A variety of 1- and 3-substituted alkylindenes (R = H, Me, Et, tert-butyl, Me(3)Si) as well as 2-methylindene and 3-(methylthio)indene have been prepared in good yields. The substituted indenes were converted into trimethylsilyl derivatives via reactions of intermediate organolithium complexes with chlorotrimethylsilane. The corresponding titanium complexes, (R-Ind)TiCl3, were synthesized in excellent yield from reactions of the trimethylsilyl derivatives with TiCl4. The titanium complexes were evaluated as styrene polymerization catalysts in toluene solution when activated by methylaluminoxane. Activities increased in the order: Cp < H(4)Ind < Ind < 1-(Me)Ind < 2-(Me)Ind. A steep drop in activity was observed when R = Et, tert-butyl, and Me(3)Si, corresponding to an increase in the steric bulk of the substituent in the catalyst precursor. 1-(MeS)IndTiCl(3) was found to be ineffective as a styrene polymerization catalyst. Syndiospecificities of the titanium complexes were generally very good (65-98%).

  DOI：

  10.1016/s0022-328x(96)06153-0