Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (18): 1909-1916.DOI: 10.6023/A12060342 Previous Articles     Next Articles

Article

边臂修饰的水杨醛亚胺第四族金属配合物的合成、结构及其乙烯聚合行为研究

王新科a,b, Sit Met-Metc, 孙杰a, 唐勇a, 谢作伟b,c   

  1. a 金属有机化学国家重点实验室 中国科学院上海有机化学研究所 上海 200032;
    b 沪港化学合成联合实验室 中国科学院上海有机化学研究所 上海 200032;
    c 香港中文大学化学系 香港新界沙田
  • 收稿日期:2012-06-25 出版日期:2012-09-28 发布日期:2012-08-14
  • 通讯作者: 唐勇,谢作伟
  • 基金资助:

    项目受国家自然科学基金(No. 20932008)、国家自然科学基金/香港资助局(No. N_CUHK470/10 to ZX and No. 21061160493 to TY)和中国科学院-求槎基金(No. GJHZ200816)资助.

Synthesis, Structure and Ethylene Polymerization Behavior of Group 4 Metal Complexes Bearing Salicylaldaminato Ligands with Appended Donor Functionality

Wang Xinkea,b, Sit Met-Metc, Sun Jieaa, Tang Yonga, Xie Zuoweib,c   

  1. a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China;
    b Shanghai-Hong Kong Joint Lab in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China;
    c Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China
  • Received:2012-06-25 Online:2012-09-28 Published:2012-08-14
  • Supported by:

    Supporting information for this article is available free of charge via the Internet at http://sioc-journal.cn Project supported by the National Natural Science Foundation of China (No. 20932008), NSFC/RGC Joint Research Scheme (No. N_CUHK470/10 to ZX and No. 21061160493 to TY) and the CAS-Croucher Funding Scheme (No. GJHZ200816).

A series of group 4 metal complexes were synthesized by an equimolar reaction of M(CH2Ph)4 with (E)-2,4-di-tert-butyl-6-[(phenylimino)methyl]phenol bearing donor functionality. This process involved toluene elimination followed by an intramolecular migration reaction of one benzyl group from metal to the imino carbon, which was supported by the isolation and structural characterization of the intermediate. These new complexes were fully characterized by multinuclear NMR spectroscopy, elemental analyses and X-ray analyses. The titanium complexes showed a very high activity in both ethylene polymerization and ethylene/1-hexene copolymerization upon activation with modified methylaluminoxane (MMAO), whereas the corresponding zirconium and hafnium complexes were almost inactive under the same reaction conditions.

Key words: ethylene polymerization, ethylene/1-hexene copolymerization, group 4 metal complex, salicylaldaminato, intramolecular migration