Synthesis, structural investigations and ethylene polymerization of titanium complexes with tripodal oxazoline ligands

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• 作者：Muhammad Hafeez ; Sonja Lippert ; Tobias Bauer…
• 关键词：Amido ligands ; Amidinates ; Aminopyridinates ; N ; ligands ; Olefin polymerization ; Oxazoline ; Titanium
• 刊名：Journal of the Iranian Chemical Society
• 出版年：2015
• 出版时间：June 2015
• 年：2015
• 卷：12
• 期：6
• 页码：957-966
• 全文大小：415 KB
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• 作者单位：Muhammad Hafeez (1)
  Sonja Lippert (2)
  Tobias Bauer (2)
  Winfried P. Kretschmer (2)
  
  1. Department of Chemistry, University of Azad Jammu and Kashmir, Muzaffarabad Azad Kashmir, 13100, Pakistan
  2. Lehrstuhl für Anorganische Chemie II, Universit?t Bayreuth, 95440, Bayreuth, Germany
  
• 刊物主题：Analytical Chemistry; Inorganic Chemistry; Physical Chemistry; Biochemistry, general; Organic Chemistry;
• 出版者：Springer Berlin Heidelberg
• ISSN：1735-2428

文摘

A series of tripodal nitrogen containing ligands including amidine and aminopyridines with extra oxazoline functionality were synthesized. The corresponding titanium complexes bearing such ligands were synthesized by diethylamine elimination route. Diethylamidotitanium trichloride [Et₂NTiCl₃] reacts with the functionalized anilines, 2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-N-(2-fluorophenyl)-aniline (FOxH) and 2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-N-(2-methoxyphenyl)aniline (MeOOxH), the amidine(E)-N-(2,6-diisopropylphenyl)-N-(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl)benzimidamide ( Am OxH), and the aminopyridines N-(2-(4,4-dimethyl-4,5-dihydro oxazol-2-yl)phenyl)-6-(piperidin-1-yl)pyridin-2-amine (ApOxH) and N-(2-(4,4- dimethyl- 4,5-dihydrooxazol-2-yl)phenyl)-6-(2,4,6-triisopropyl phenyl)pyridin-2-amine (Ap*OxH), under diethylamine elimination to form the corresponding titanium trichlorides [FOxTiCl3], [MeOOxTiCl3], [AmOxTiCl3], [ApOxTiCl3] and [Ap*OxTiCl3] in excellent yields. These compounds were characterized by spectroscopic methods, and X-ray crystal structure analysis (selected complexes). Furthermore, their behavior in ethylene polymerization was explored. The complexes show moderate activity towards ethylene if activated with MAO. The observed PEs were analyzed by HT-GPC and were found to be of low molecular weight for the amidinate AmOxTiCl3 but of very high one (Mp up to 3.5 million g/mol) for the aminopyridinate Ap*OxTiCl3 titanium complex.