[Ti2(O-i-Pr)2((O-2,4-Me2C6H2-6-CH2)2(μ2-OCH2CH2)N)2] | 934666-44-1

• 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: [Ti2(O-i-Pr)2((O-2,4-Me2C6H2-6-CH2)2(μ2-OCH2CH2)N)2]
• 英文别名: 2-[[(3,5-Dimethyl-2-oxidophenyl)methyl-(2-oxidoethyl)amino]methyl]-4,6-dimethylphenolate;propan-2-olate;titanium(4+)
• CAS: 934666-44-1
• 化学式: C₄₆H₆₂N₂O₈Ti₂
• 分子量: 866.767
• InChiKey: MVYDSEKMGXCZJW-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  2.37
• 重原子数：
  58
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  191
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  [Ti2(O-i-Pr)2((O-2,4-Me2C6H2-6-CH2)2(μ2-OCH2CH2)N)2] 、 三甲基铝 以 乙醚 、 甲苯 为溶剂， 以97%的产率得到[TiMe((O-2,4-Me2C6H2-6-CH2)2(μ2-OCH2CH2)N)(Me2Al(μ2-O-i-Pr))]
  参考文献：
  名称：

  Synthesis and Structure of Titanatranes Containing Tetradentate Trianionic Donor Ligands of the Type [(O-2,4-R₂C₆H₂-6-CH₂)₂(OCH₂CH₂)]N^3- and Their Use in Catalysis for Ethylene Polymerization

  摘要：

  Syntheses and structural characterizations of various titanatranes containing bis(aryloxo)ethanolamine ligands of the type [(O-2,4-R2C6H2-6-CH2)(2)(OCH2CH2)]N3- (R = Me, Bu-t) have been explored. The reaction of [(HO-2,4-Me2C6H2-6-CH2)(2)(HOCH2CH2)]N with Ti(OR')(4) in toluene afforded dimeric titanatranes, Ti-2(OR')(2){[(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-OCH2CH2)]N}(2) [R' = Pr-i (1a), Bu-t (1b)], in high yields. Crystallographic analyses of 1a,b indicate that these complexes have a distorted octahedral geometry around Ti, and the O atom in the alkoxo ligand is coordinated to two Ti atoms. The similar reactions of [(HO-2,4-(Bu2C6H2)-Bu-t-6-CH2)(2)(HOCH2CH2)]N with Ti(OR')(4) afforded the monomeric titanatranes Ti(OR')[(O-2,4-(Bu2C6H2)-Bu-t-6-CH2)(2)(OCH2CH2)]N (2a,b) in high yields; these complexes have a rather distorted trigonal bipyramidal structure around Ti consisting of a plane formed by two aryloxo and one alkoxo ligand and an N-Ti-O (in (OBu)-Bu-t) axis determined by the X-ray crystallographic analyses. The reaction of 1a,b with 2.0 equiv of AlMe3 (1.0 equiv per Ti) in toluene gave the Ti-Me complexes coordinated to Me2Al(OR'), {TiMe[(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-OCH2CH2)N]}[Me2Al(mu(2)-OR')] [R' = Pr-i (3a), Bu-t (3b)], in exclusive yields, and these complexes were identified by H-1 and C-13 NMR spectra, elemental analyses, and X-ray crystallography. Complexes 1a and 2b exhibited moderate catalytic activities for ethylene polymerization at 100-120 degrees C in the presence of methylaluminoxane (MAO), and the activity increased upon the addition of a small amount of AlMe3. Similar catalytic activities were observed by using 3a,b in the presence of MAO, affording high molecular weight polyethylene with unimodal molecular weight distributions. Ethylene polymerization in octane by 3b took place without additional cocatalyst at 120 degrees C with moderate catalytic activity (94 kg PE/mol Ti center dot h), affording high molecular weight polymer with unimodal distribution (M-w = 1.00 x 10(6), M-w/M-n = 2.58). The result clearly suggests that the cationic species formed by cleavage of the Ti-O bonds plays an important role as the active species for the polymerization.

  DOI：

  10.1021/om0611507
• 作为产物：
  描述：

  titanium(IV) isopropylate 、 N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-2-aminoethanol 以 甲苯 为溶剂， 以86%的产率得到[Ti2(O-i-Pr)2((O-2,4-Me2C6H2-6-CH2)2(μ2-OCH2CH2)N)2]
  参考文献：
  名称：

  Synthesis and Structure of Titanatranes Containing Tetradentate Trianionic Donor Ligands of the Type [(O-2,4-R₂C₆H₂-6-CH₂)₂(OCH₂CH₂)]N^3- and Their Use in Catalysis for Ethylene Polymerization

  摘要：

  Syntheses and structural characterizations of various titanatranes containing bis(aryloxo)ethanolamine ligands of the type [(O-2,4-R2C6H2-6-CH2)(2)(OCH2CH2)]N3- (R = Me, Bu-t) have been explored. The reaction of [(HO-2,4-Me2C6H2-6-CH2)(2)(HOCH2CH2)]N with Ti(OR')(4) in toluene afforded dimeric titanatranes, Ti-2(OR')(2){[(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-OCH2CH2)]N}(2) [R' = Pr-i (1a), Bu-t (1b)], in high yields. Crystallographic analyses of 1a,b indicate that these complexes have a distorted octahedral geometry around Ti, and the O atom in the alkoxo ligand is coordinated to two Ti atoms. The similar reactions of [(HO-2,4-(Bu2C6H2)-Bu-t-6-CH2)(2)(HOCH2CH2)]N with Ti(OR')(4) afforded the monomeric titanatranes Ti(OR')[(O-2,4-(Bu2C6H2)-Bu-t-6-CH2)(2)(OCH2CH2)]N (2a,b) in high yields; these complexes have a rather distorted trigonal bipyramidal structure around Ti consisting of a plane formed by two aryloxo and one alkoxo ligand and an N-Ti-O (in (OBu)-Bu-t) axis determined by the X-ray crystallographic analyses. The reaction of 1a,b with 2.0 equiv of AlMe3 (1.0 equiv per Ti) in toluene gave the Ti-Me complexes coordinated to Me2Al(OR'), {TiMe[(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-OCH2CH2)N]}[Me2Al(mu(2)-OR')] [R' = Pr-i (3a), Bu-t (3b)], in exclusive yields, and these complexes were identified by H-1 and C-13 NMR spectra, elemental analyses, and X-ray crystallography. Complexes 1a and 2b exhibited moderate catalytic activities for ethylene polymerization at 100-120 degrees C in the presence of methylaluminoxane (MAO), and the activity increased upon the addition of a small amount of AlMe3. Similar catalytic activities were observed by using 3a,b in the presence of MAO, affording high molecular weight polyethylene with unimodal molecular weight distributions. Ethylene polymerization in octane by 3b took place without additional cocatalyst at 120 degrees C with moderate catalytic activity (94 kg PE/mol Ti center dot h), affording high molecular weight polymer with unimodal distribution (M-w = 1.00 x 10(6), M-w/M-n = 2.58). The result clearly suggests that the cationic species formed by cleavage of the Ti-O bonds plays an important role as the active species for the polymerization.

  DOI：

  10.1021/om0611507