[Ti(OiPr)(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))] | 350484-88-7

• 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: [Ti(OiPr)(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))]
• 英文别名: Ti(OⁱPr)[{(O-2,4-^tBu₂C₆H₂)-6-CH₂}₃N]；(N(CH2C6H2(C(CH3)3)2O)3)Ti(O-i-Pr)；Ti(iso-propylate)[(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine)(-3H)]；2-[[Bis[(3,5-ditert-butyl-2-oxidophenyl)methyl]amino]methyl]-4,6-ditert-butylphenolate;propan-2-olate;titanium(4+)；2-[[bis[(3,5-ditert-butyl-2-oxidophenyl)methyl]amino]methyl]-4,6-ditert-butylphenolate;propan-2-olate;titanium(4+)
• CAS: 350484-88-7
• 化学式: C₄₈H₇₃NO₄Ti
• 分子量: 775.992
• InChiKey: IKLKOVPQGSSWOZ-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  9.65
• 重原子数：
  54
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  95.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [Ti(OiPr)(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))] 、 二甲基氯化铝 以 正己烷 、 甲苯 为溶剂， 反应 2.0h， 以63.8%的产率得到[TiCl(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))]
  参考文献：
  名称：

  Effect of Terminal Aryloxo Ligands in Ethylene Polymerization Using Titanatranes of the Type, [Ti(OAr){(O-2,4-R₂C₆H₂)-6-CH₂}₃N]: Synthesis and Structural Analysis of the Heterobimetallic Complexes of Titanatranes with AlMe₃

  摘要：

  Effects of aryloxo terminal ligands and AlMe3 in ethylene polymerization using a series of Ti(OAr)[{(O-2,4-R2C6H2)-6-CH2}(3)N] [R = Me (1), Bu-t (2); Ar = 2,6-Me2C6H3 (a), 2,6-(Pr2C6H3)-Pr-i (b), 2,6-Ph2C6H3 (c), 2,6-F2C6H3 (d), C6F5 (e)] (1a-1e, 2d,2e) in the presence of methylaluminoxane (MAO) have been explored. Reactions of 1b,1d,1e, which showed an increase in the activity upon addition of a small amount of AlMe3, with 1.0 equiv of AlMe3 afforded heterobimetallic Ti-Al complexes, TiMe(O-2,6-(Pr2C6H3)-Pr-i) [(O-2,4-Me2C6H2-6-CH2)(mu(2)-O-2,4-Me2C6H2-6-CH2)(Me2Al-mu(2)-O-2,4-Me2C6H2-6-CH2)N] (3b) and [TiMe{(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-O-2,4-Me2C6H2-6-CH2)N}][Me2Al(mu(2)-OAr)] [Ar = 2,6-F2C6H3 (3d), C6F5 (3e)], in moderate yields, and their structures were determined by X-ray crystallography. In contrast, the similar reaction of la (which showed a decrease in the activity upon addition of AlMe3) yielded [Al(mu(2)-O-2,6-C6H3)Me-2](2) and TiMe[{(O-2,4-Me2C6H2)-6-CH2}(3)N] as isolated forms: [Al(mu(2)-OC6F5)Me-2](2) was isolated from the mixture in the reactions of 1c,2d,2e. The isolated heterobimetallic complexes (3b,3d,3e) exhibited high catalytic activities for ethylene polymerization in the presence of MAO, suggesting that these bimetallic species play a role in this catalysis.

  DOI：

  10.1021/om3008635
• 作为产物：
  描述：

  2,4-二叔丁基苯酚 在 对甲苯磺酸 作用下， 以 四氢呋喃 为溶剂， 反应 56.0h， 生成 [Ti(OiPr)(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))]
  参考文献：
  名称：

  Ti（IV）-Tris（酚盐）催化剂体系，用于环氧乙烷和二氧化碳的开环共聚。

  摘要：

  氨基三（酚盐）配体（LTiX，X =氯化物，异丙醇）的钛（IV）配合物与双（三苯基膦）亚胺氯化物（PPNCl）一起是用于二氧化碳和环己烯的开环共聚的活性催化剂体系。它们表现出适度的活性，周转频率值约为60 h-1（0.02 mol％的催化剂，80°C，40 bar的CO2）和高选择性（碳酸盐键> 90％），但它们的绝对性能低于那些最活跃的Ti（IV）催化剂体系。反应随着聚碳酸酯（PCHC）摩尔质量与环氧化物的转化而线性发展，这与受控聚合相一致，并发展出PCHC的双峰摩尔质量分布（最高M n = 42 kg mol-1）。[LTiO i Pr]与氯化四苯基chloridePPh4Cl之间的化学计量反应 可以分离假定的催化中间体[LTi（O i Pr）Cl]-，该中间体使用单晶X射线衍射技术表征。提出了阴离子钛络合物[LTi（OR）Cl]-作为催化循环中醇盐中间体的扩散模型。

  DOI：

  10.1021/acs.organomet.9b00845

文献信息

• Highly active and stereoselective zirconium and hafnium alkoxide initiators for solvent-free ring-opening polymerization of rac-lactide
  作者：Amanda J. Chmura、Matthew G. Davidson、Catherine J. Frankis、Matthew D. Jones、Matthew D. Lunn

  DOI：10.1039/b718678a

  日期：——

  Under solvent-free conditions (at 130 degrees C), zirconium and hafnium amine tris(phenolate) alkoxides are extremely active, well-controlled, single-site initiators for the ring-opening polymerization of rac-lactide, yielding highly heterotactic polylactide.

  在无溶剂条件下（在130摄氏度下），锆胺和胺三（酚盐）醇盐是非常活泼，控制良好的单中心引发剂，可用于外消旋丙交酯的开环聚合反应，产生高度杂规的聚丙交酯。
• Hetero-bimetallic Complexes of Titanatranes with Aluminum Alkyls: Synthesis, Structural Analysis, and Their Use in Catalysis for Ethylene Polymerization
  作者：Prabhuodeyara M. Gurubasavaraj、Kotohiro Nomura

  DOI：10.1021/om100119g

  日期：2010.8.23

  Hetero-bimetallic Ti−Al complexes containing tris(aryloxo)amine ligands of type [TiR′(μ2-O-2,4-R2C6H2-6-CH2)(O-2,4-R2C6H2-6-CH2)2N}][R′2Al(μ2-OiPr)] [3a,b and 4a; R = Me (3), tBu (4); R′ = Me (a), Et (b)] have been prepared by reacting Ti(OiPr)[(O-2,4-R2C6H2-6-CH2)3N] [R = Me (1), tBu (2)] with 1.0 equiv of AlR′3 in toluene. Crystallographic analyses of 3a,b and 4a reveal that these complexes have

  含有式[TIR'的三（芳氧）胺配体的杂双金属的Ti-Al系复合物（μ 2 -O-2,4-R 2 c ^ 6 ħ 2 -6-CH 2）（O-2,4-R 2 ç 6 ħ 2 -6-CH 2）2 N}] [R' 2的Al（μ 2 -O我PR）] [图3a，b和图4a ; R = Me（3），t Bu（4）; R'= Me（a），Et（b）]是通过使Ti（O i Pr）[（O-2,4-R 2c ^ 6 ħ 2 -6-CH 2）3 N] [R =我（1），吨卜（2）]用1.0当量为AlR的' 3在甲苯中。3a，b和4a的晶体学分析表明，这些配合物在Ti周围具有扭曲的八面体几何形状，在Al周围具有扭曲的四面体几何形状。络合物3a，b和4a在80-120°C的甲基铝氧烷（MAO）存在下对甲苯中的乙烯聚合反应表现出适度的催化活性，而4a则比3a表现出更高的活性，b。的叔丁基类似物（图4a）本身聚合乙烯而
• Synthesis of Titanium Complexes Containing an Amine Triphenolate Ligand of the Type [TiX{(O-2,4-R₂C₆H₂)-6-CH₂}₃N] and the Ti–Al Heterobimetallic Complexes with AlMe₃: Effect of a Terminal Donor Ligand in Ethylene Polymerization
  作者：Kotohiro Nomura、Udomchai Tewasekson、Yuki Takii

  DOI：10.1021/acs.organomet.5b00303

  日期：2015.7.13

  The synthesis of various titanatranes containing tris(aryloxo)amine ligands, TiX[(O-2,4-R2C6H2)-6-CH2}(3)N] [R = Me (1), Bu-t (2); X = (OPr)-Pr-i (a), (OBu)-Bu-t (b), OCH(CF3)(2) (c), OC(CF3)(3) (d), Cl (e)], and some reactions with Al alkyls have been explored. The Ti-Al heterobimetallic complexes [TiMe(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-O-2,4-Me-2-C6H2-6-CH2)}N-[NMe2Al(mu(2)-OR')] [R' = Bu-t (3b), CH-(CF3)(2) (3c), C(CF3)(3) (3d)] were isolated by reaction of 1b-d with 1 equiv of AlMe3, whereas reaction of 2b with AlMe3 in toluene did not take place under the same conditions and the reaction of 2c afforded the methyl complex TiMe[(O-2,4-(Bu2C6H2)-Bu-t)-6-CH2}(3)N]. Structures of 3b,c were determined by X-ray crystallography. These complexes exhibited high catalytic activities for ethylene polymerization in n-octane in the presence of MAO, and the activity by 1 and 2 was affected by the terminal donor ligand (X) as well as the substituent on the atrane ligand (R). The activities by 1c,d increased upon addition of AlMe3, and the corresponding heterobimetallic complexes (3c,d) showed high activities, whereas an increase in the activity upon addition of AlMe3 was not observed by 1b,e, and 2c,e.
• Ti(IV)–Tris(phenolate) Catalyst Systems for the Ring-Opening Copolymerization of Cyclohexene Oxide and Carbon Dioxide
  作者：Sumesh K. Raman、Arron C. Deacy、Leticia Pena Carrodeguas、Natalia V. Reis、Ryan W. F. Kerr、Andreas Phanopoulos、Sebastian Morton、Matthew G. Davidson、Charlotte K. Williams

  DOI：10.1021/acs.organomet.9b00845

  日期：2020.5.11

  Titanium(IV) complexes of amino-tris(phenolate) ligands (LTiX, X = chloride, isopropoxide) together with bis(triphenylphosphine)iminium chloride (PPNCl) are active catalyst systems for the ring-opening copolymerization of carbon dioxide and cyclohexene oxide. They show moderate activity, with turnover frequency values of ∼60 h-1 (0.02 mol % of catalyst, 80 °C, 40 bar of CO2) and high selectivity (carbonate

  氨基三（酚盐）配体（LTiX，X =氯化物，异丙醇）的钛（IV）配合物与双（三苯基膦）亚胺氯化物（PPNCl）一起是用于二氧化碳和环己烯的开环共聚的活性催化剂体系。它们表现出适度的活性，周转频率值约为60 h-1（0.02 mol％的催化剂，80°C，40 bar的CO2）和高选择性（碳酸盐键> 90％），但它们的绝对性能低于那些最活跃的Ti（IV）催化剂体系。反应随着聚碳酸酯（PCHC）摩尔质量与环氧化物的转化而线性发展，这与受控聚合相一致，并发展出PCHC的双峰摩尔质量分布（最高M n = 42 kg mol-1）。[LTiO i Pr]与氯化四苯基chloridePPh4Cl之间的化学计量反应 可以分离假定的催化中间体[LTi（O i Pr）Cl]-，该中间体使用单晶X射线衍射技术表征。提出了阴离子钛络合物[LTi（OR）Cl]-作为催化循环中醇盐中间体的扩散模型。
• Effect of Terminal Aryloxo Ligands in Ethylene Polymerization Using Titanatranes of the Type, [Ti(OAr){(O-2,4-R₂C₆H₂)-6-CH₂}₃N]: Synthesis and Structural Analysis of the Heterobimetallic Complexes of Titanatranes with AlMe₃
  作者：Yuki Takii、Prabhuodeyara M. Gurubasavaraj、Shohei Katao、Kotohiro Nomura

  DOI：10.1021/om3008635

  日期：2012.12.10

  Effects of aryloxo terminal ligands and AlMe3 in ethylene polymerization using a series of Ti(OAr)[(O-2,4-R2C6H2)-6-CH2}(3)N] [R = Me (1), Bu-t (2); Ar = 2,6-Me2C6H3 (a), 2,6-(Pr2C6H3)-Pr-i (b), 2,6-Ph2C6H3 (c), 2,6-F2C6H3 (d), C6F5 (e)] (1a-1e, 2d,2e) in the presence of methylaluminoxane (MAO) have been explored. Reactions of 1b,1d,1e, which showed an increase in the activity upon addition of a small amount of AlMe3, with 1.0 equiv of AlMe3 afforded heterobimetallic Ti-Al complexes, TiMe(O-2,6-(Pr2C6H3)-Pr-i) [(O-2,4-Me2C6H2-6-CH2)(mu(2)-O-2,4-Me2C6H2-6-CH2)(Me2Al-mu(2)-O-2,4-Me2C6H2-6-CH2)N] (3b) and [TiMe(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-O-2,4-Me2C6H2-6-CH2)N}][Me2Al(mu(2)-OAr)] [Ar = 2,6-F2C6H3 (3d), C6F5 (3e)], in moderate yields, and their structures were determined by X-ray crystallography. In contrast, the similar reaction of la (which showed a decrease in the activity upon addition of AlMe3) yielded [Al(mu(2)-O-2,6-C6H3)Me-2](2) and TiMe[(O-2,4-Me2C6H2)-6-CH2}(3)N] as isolated forms: [Al(mu(2)-OC6F5)Me-2](2) was isolated from the mixture in the reactions of 1c,2d,2e. The isolated heterobimetallic complexes (3b,3d,3e) exhibited high catalytic activities for ethylene polymerization in the presence of MAO, suggesting that these bimetallic species play a role in this catalysis.