[(OC6H3-2-t-Bu-6-CH=NC6F5)TiCl3(THF)] | 848616-68-2

• 英文名称: [(OC6H3-2-t-Bu-6-CH=NC6F5)TiCl3(THF)]
• 英文别名: TiCl3(3-tBu-2-OC6H3CHNC6F5)(tetrahydrofuran)
• CAS: 848616-68-2
• 化学式: C₂₁H₂₁Cl₃F₅NO₂Ti
• 分子量: 568.634
• InChiKey: VWEWXPONMBYESQ-QZOJUGOSSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(OC6H3-2-t-Bu-6-CH=NC6F5)TiCl3(THF)] 、 potassium 4-phenylamino-3-penten-2-onate 以 二氯甲烷 为溶剂， 以51%的产率得到
  参考文献：
  名称：

  The synthesis, structure and ethene polymerization activity of octahedral heteroligated (salicylaldiminato)(β-enaminoketonato)titanium complexes: The X-ray crystal structure of {3-But-2-(O)C6H3CHN(Ph)}{(Ph)NC(Me)C(H)C(Me)O}TiCl2

  摘要：

  Treatment of the mono(salicylaldiminato)titanium complexes {3-Bu'-2-(O)C6H3CHN(Ar)}TiCl3(THF) (Ar = C6H5, 2,4,6-Me3C6H2 or C6F5) with the potassium beta-enaminoketonates (C6H5)NC(CH3)C(H)C(R)OK (R = CH3, CF3) yielded the first examples of heteroligated (salicylaldiminato) (beta-enaminoketonato)titanium dichloride complexes. The complex {3-Bu'-2-(O)C6H3CHN(C6H5)}{(C6H5)-NC(CH3)C(H)C(CH3)O}TiCl2 was structurally characterized by X-ray diffraction and has an orientation with trans-O,O,cis-Cl,Cl, cis-N,N distorted octahedral geometry. These complexes polymerize ethene when activated with MAO; the highest productivity, 5650 kg PE (mol metal)(-1) h(-1) atm(-1), was afforded by {3-Bu'-2-(O)C6H3CHN(C6F5)} {(C6H5)NC(CH3)C(H)C(CF3)O}TiCl2 at 60 degrees C. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.03.026
• 作为产物：
  描述：

  tetrachlorobis(tetrahydrofuran)titanium(IV) 、 3-Bu(t)-2-(OSiMe3)C6H3CH=NC6F5 以 二氯甲烷 为溶剂， 生成 [(OC6H3-2-t-Bu-6-CH=NC6F5)TiCl3(THF)]
  参考文献：
  名称：

  The synthesis, structure and ethene polymerisation catalysis of mono(salicylaldiminato) titanium and zirconium complexes

  摘要：

  硅醚3-But-2-(OSiMe3)C6H3CHNR（2a-e）通过已知的亚胺酚（1a-e）去质子化并与SiClMe3处理制备而成（a，R=C6H5；b，R=2,6-Pri2C6H3；c，R=2,4,6-Me3C6H2；d，R=2-C6H5C6H4；e，R=C6F5）。2a-c与TiCl4在烃溶剂中反应生成双核配合物[Ti{3-But-2-(O)C6H3CHN(R)}Cl(µ-Cl3)TiCl3]（3a-c）。五氟苯基物种2e与TiCl4反应生成已知配合物Ti{3-But-2-(O)C6H3CHN(R)}2Cl2。通过反复重结晶3c，分离出单核五配位配合物Ti{3-But-2-(O)C6H3CHN(2,4,6-Me3C6H2)}Cl3（4c）。在四氢呋喃的存在下进行去卤硅化反应，得到八面体、单核配合物Ti{3-But-2-(O)C6H3CHN(R)}Cl3(THF)（5a-e）。与ZrCl4(THF)2的反应类似，生成配合物Zr{3-But-2-(O)C6H3CHN(R)}Cl3(THF)（6b-e）。已确定3b、4c、5a、5c、5e、6b、6d、6e以及水杨醛钛配合物Ti{3-But-2-(O)C6H3CHO}Cl3(THF)（7）的晶体结构。用MAO在乙烯饱和的甲苯溶液中激活5a-e和6b-e配合物可生成聚乙烯，其活性高低取决于亚胺取代基。

  DOI：

  10.1039/b414229b

文献信息

• Novel heteroligated titanium complexes with fluorinated salicylaldiminato and β-enaminoketonato ligands: synthesis, characterization and catalytic behavior in vinyl addition polymerization of norbornene
  作者：Ying-Yun Long、Wei-Ping Ye、Ping Tao、Yue-Sheng Li

  DOI：10.1039/c0dt01225d

  日期：——

  The X-ray crystallographic analysis indicated these complexes adopted a distorted octahedral geometry around the titanium center. Upon activation with modified methylaluminoxane, complexes 3a–g exhibited moderate to good catalytic activity for norbornene (NB) vinyl addition polymerization, producing moderate molecular weight polynorbornenes under mild conditions. The introduction of electron-withdrawing

  一系列通式为[3-Bu t -2-OC 6 H 3 CH N（C 6 F 5）] [PhN C（CF 3）CHC（R）的杂合的（水杨基亚氨基）（β-烯氨基酮基）钛配合物O] TiCl 2（3a：R Ph，3b：R C 6 H 4 Ph（p），3c：R C 6 H 4 Ph（o），3d：R = 1-萘基，3e：R = C 6 H 4 F 2（2，6），3f：R ＝ C 6 H 4 Cl 2（2，5），3g：R C 6 F 4（2，3，5，6）OMe（4）。配合物3d，3f–g的结构通过单晶X射线衍射分析确定。X射线晶体学分析表明这些络合物在钛中心周围采用了扭曲的八面体几何形状。经修饰的甲基铝氧烷活化后，配合物3a–g表现出中等至良好的催化活性。降冰片烯（NB）乙烯基加成聚合反应，在温和条件下产生中等分子量的聚降冰片烯。吸电子基团的引入可以大大提高催化活性。重要的是，杂化的钛配合物与同等的对应
• Hybrid catalysts: the synthesis, structure and ethene polymerisation activity of (salicylaldiminato)(pyrrolylaldiminato) titanium complexes
  作者：Dale A. Pennington、Simon J. Coles、Michael B. Hursthouse、Manfred Bochmann、Simon J. Lancaster

  DOI：10.1039/b504113a

  日期：——

  pyrrolylaldiminato ligand, K[2-(C6H5NCH)C4H3N], to afford the first examples of hybrid salicylaldiminato-ligated octahedral titanium complexes; the pre-catalysts give from very high to extremely high ethene polymerisation productivities when activated with MAO.

  单（水杨基铝亚氨基）络合物Ti 3-tBu-2-（O）C6H3CH = N（R）} Cl3（THF）（其中R = C6H5，C6F5）与金属化的吡咯基铝亚氨基配体K [2-（ NCH）反应[C4H3N]，以提供杂化的水杨基亚氨基连接的八面体钛络合物的第一个实例；当用MAO活化时，预催化剂可提供极高的乙烯聚合生产率。
• Homo- and Heteroligated Salicylaldiminato Titanium Complexes with Different Substituents <i>Ortho</i> to the Phenoxy Oxygens for Ethylene and Ethylene/1-Hexene (Co)polymerization
  作者：Erdong Yao、Jianchun Wang、Zhongtao Chen、Yuguo Ma

  DOI：10.1021/ma5017677

  日期：2014.12.9

  A series of homoligated (1c-1e) and heteroligated (2a-2e) salicylaldiminato titanium dichloride complexes with different substituents ortho to the phenoxy oxygens were efficiently prepared. X-ray diffraction studies on these new dichloride complexes 2b, 2d, and 2e reveal a distorted octahedral coordination of the central metal. In the presence of dried methylaluminoxane, all the complexes exhibit high ethylene polymerization productivities. Surprisingly, complex 1d incorporating an o-(trimethylsilyl)ethynyl group displays the highest activity [5.26 X 10(3) kg of polyethylenes (mol Ti)(-1) h(-1)]. In ethylene/1-hexene copolymerization, the heteroligated complexes 2a-2e display improved activities and intermediate incorporation ability compared with their homoligated counterparts 1a-1f. The activity and incorporation ability for 1-hexene are highly dependent on the nature of the ortho-substituents. Among them, (trimethylsilyl)ethynyl-substituted precatalyst (1d) achieves the highest incorporation ratio (27.3 mol %), while ethynyl-substituted precatalyst (2c) achieves the highest copolymerization activity [2.89 X 10(3) kg of copolymers (mol Ti)(-1) h(-1)].
• Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations
  作者：Lewis M. Broomfield、Yann Sarazin、Joseph A. Wright、David L. Hughes、William Clegg、Ross W. Harrington、Manfred Bochmann

  DOI：10.1016/j.jorganchem.2007.04.047

  日期：2007.10

  Treatment of MCl3(OC6H3-2-'Bu-6-CH=NC6F5)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K+[RN=CHC4H3N](-)), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl2(N-O)(N-N). The molecular structures of TiCl2(OC6H3-2-'Bu-6-CH=NC6F5)(C2H5N=CHC4H3N) (1c), TiCl2(OC6H3-2-'Bu-6-CH=NC6F5)(C6H11N=CHC4H3N) (1b) and ZrCl2(OC6H3-2-'Bu-6-CH=NC6F5)(C6H11N=CHC4H3N) (2b) show distorted octahedral geometries with trans-O-,N-/cis-Cl-2 arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene-propylene copolymers show ca. 80% 1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure. (C) 2007 Elsevier B.V. All rights reserved.