bis[N-phenylpyrrolylaldiminato]titanium(IV) dichloride | 274687-26-2

• 英文名称: bis[N-phenylpyrrolylaldiminato]titanium(IV) dichloride
• CAS: 274687-26-2
• 化学式: C₂₂H₁₈Cl₂N₄Ti
• 分子量: 457.198
• InChiKey: GPYVLTCYRLUYJL-UBTFDZPSSA-L

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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  bis[N-phenylpyrrolylaldiminato]titanium(IV) dichloride 在 ⁽¹³⁾C-methylalumoxane 作用下， 以 further solvent(s) 为溶剂， 生成 (N-phenylpyrrolylaldiminato)2Ti((13)CH3)Cl
  参考文献：
  名称：

  甲基铝氧烷活化双（吡咯烷基二甲氨基）和（水杨基醛二甲氨基）（吡咯基乙二氨基）钛聚合催化剂

  摘要：

  活化基于二氯化双[ N-苯基吡咯烷基二钛（IV）（L 2 TiCl 2，I）和[ N-（3-叔丁基水杨基）-2,3,4,5的烯烃聚合催化剂后形成的阳离子中间体已经鉴定出具有甲基铝氧烷（MAO）的二氯化6-6-五氟苯胺基-N'-苯基吡咯烷基铝二钛（IV）（L'LTiCl 2，II）。[L 2 TiMe（S）] + [MeMAO] -和[L'LTiMe（S）] + [MeMAO] -能够进行乙烯聚合的外层离子对的特征在于1 H和13 C NMR光谱。与甲基金属茂阳离子不同的是，第一个乙烯插入这些物种的Ti-Me键的势垒不会显着高于后续插入的势垒。出人意料的是，尽管在MAO存在下均化的催化剂前体L 2 TiCl 2易于将配体转移至铝，但在相同条件下，杂化体系L'LTiCl 2 / MAO证明对配体抗扰性。

  DOI：

  10.1021/om0607752
• 作为产物：
  描述：

  四氯化钛 、 N-pyrrol-2-ylmethylene-aniline 在 n-butyl lithium 作用下， 以 乙醚 、 正己烷 、 正庚烷 为溶剂， 以79%的产率得到bis[N-phenylpyrrolylaldiminato]titanium(IV) dichloride
  参考文献：
  名称：

  New Titanium Complexes Having Two Pyrrolide−Imine Chelate Ligands:  Syntheses, Structures, and Ethylene Polymerization Behavior

  摘要：

  New titanium complexes 1-4 having two nonsymmetric bidentate pyrrolide-imine chelate ligands, [2-(RNCH)C4H3N](2)TiCl2 (1, R = Ph; 2, R = Et; 3, R = n-hexyl; 4, R = cyclohexyl), are prepared in good yields from the lithium salt of the corresponding ligands and TiCl4. Complex I is suggested by DFT calculations to adopt a distorted-octahedral structure in which the two pyrrolide-N atoms are situated in trans positions, while the two imine-N atoms and the two Cl atoms are located cis to one another. The spatial disposition elucidated by X-ray crystallographic analysis of complex 1 is consistent with the preferred structure predicted by DFT calculations. The molecular structures of complexes 2 and 4 established by X-ray analyses are very similar to that of complex 1. DFT calculations suggest that an active species derived from complex 1, for ethylene polymerization, possesses cis-located active sites trans to the imine-N atoms. These complexes were investigated as ethylene polymerization catalysts. Using methylalumoxane (MAO) as a cocatalyst, these complexes display very high activities and produce high-molecular-weight polyethylenes. Among them, complex 4 exhibits the highest activity (14 100 kg of polymer/((mol of Ti) h) comparable to that of Cp2TiCl2 with a very high molecular weight (M-v) value of 2 601 000. Alternatively, using Ph3CB(C6F5)(4)/i-Bu3Al as a cocatalyst, these complexes produce ultrahigh-molecular-weight polyethylenes (M-v > 4 000 000) with high activities (1500-2000 kg of polymer/((mol of Ti)/h).

  DOI：

  10.1021/om010468q

文献信息

• Living Copolymerization of Ethylene with Norbornene Catalyzed by Bis(Pyrrolide−Imine) Titanium Complexes with MAO
  作者：Yasunori Yoshida、Jun-ichi Mohri、Sei-ichi Ishii、Makoto Mitani、Junji Saito、Shigekazu Matsui、Haruyuki Makio、Takashi Nakano、Hidetsugu Tanaka、Mitsuhiko Onda、Yukari Yamamoto、Akira Mizuno、Terunori Fujita

  DOI：10.1021/ja048357g

  日期：2004.9.1

  Bis(pyrrolide-imine) Ti complexes in conjunction with methylalumoxane (MAO) were found to work as efficient catalysts for the copolymerization of ethylene and norbornene to afford unique copolymers via an addition-type polymerization mechanism. The catalysts exhibited very high norbornene incorporation, superior to that obtained with Me(2)Si(Me(4)Cp)(N-tert-Bu)TiCl(2) (CGC). The sterically open and highly electrophilic

  双（吡咯烷-亚胺）Ti 配合物与甲基铝氧烷 (MAO) 结合可作为乙烯和降冰片烯共聚的有效催化剂，通过加成型聚合机制提供独特的共聚物。催化剂表现出非常高的降冰片烯掺入，优于用 Me(2)Si(Me(4)Cp)(N-tert-Bu)TiCl(2) (CGC) 获得的。催化剂的空间开放和高度亲电性质可能是极好的降冰片烯掺入的原因。尽管催化剂具有 C(2) 对称性质，但催化剂显示出产生交替共聚物的明显趋势，该共聚物具有不规则立体结构。聚合介质中的降冰片烯/乙烯摩尔比对所得共聚物的分子量分布具有深远的影响。在降冰片烯/乙烯比率大于约。如图 1 所示，催化剂介导乙烯和降冰片烯的室温活性共聚，形成高分子量单分散共聚物（M(n) > 500,000，M(w)/M(n) < 1.20）。在低分子量条件下生产的共聚物的 (13) C NMR 光谱分析表明共聚是由降冰片烯插入引发的，并且催化剂在生活条件下主要