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

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Abstract

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.

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Acknowledgments

We thank the Deutsche Forschungsgemeinschaft (DFG) SFB 840 for supporting this work. Corresponding author thanks the University of Azad Jammu and Kashmir and the HEC (Higher Education Commission) Pakistan for a scholarship. We thank T. Bauer for his help in the X-ray lab.

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Authors and Affiliations

  1. Department of Chemistry, University of Azad Jammu and Kashmir, Muzaffarabad Azad Kashmir, 13100, Pakistan

    Muhammad Hafeez

  2. Lehrstuhl für Anorganische Chemie II, Universität Bayreuth, 95440, Bayreuth, Germany

    Sonja Lippert, Tobias Bauer & Winfried P. Kretschmer

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  1. Muhammad Hafeez
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  2. Sonja Lippert
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  3. Tobias Bauer
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  4. Winfried P. Kretschmer
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Correspondence to Muhammad Hafeez.

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Hafeez, M., Lippert, S., Bauer, T. et al. Synthesis, structural investigations and ethylene polymerization of titanium complexes with tripodal oxazoline ligands. J IRAN CHEM SOC 12, 957–966 (2015). https://doi.org/10.1007/s13738-014-0558-8

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  • DOI: https://doi.org/10.1007/s13738-014-0558-8

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