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Group 4 Metal Complexes That Contain a Thioether-Functionalized Phenolato Ligand: Synthesis, Structure, and 1-Hexene Polymerization

  1. Bing Lian,
  2. Klaus Beckerle,
  3. Thomas P. Spaniol,
  4. Jun Okuda

Article first published online: 2 DEC 2008

DOI: 10.1002/ejic.200800810

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2009, Issue 2, pages 311–316, January 2009

Additional Information

How to Cite

Lian, B., Beckerle, K., Spaniol, T. P. and Okuda, J. (2009), Group 4 Metal Complexes That Contain a Thioether-Functionalized Phenolato Ligand: Synthesis, Structure, and 1-Hexene Polymerization. Eur. J. Inorg. Chem., 2009: 311–316. doi: 10.1002/ejic.200800810

Author Information

  1. Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany, Fax: +49-241-80-92644

Publication History

  1. Issue published online: 29 DEC 2008
  2. Article first published online: 2 DEC 2008
  3. Manuscript Received: 14 AUG 2008

Funded by

  • Deutsche Forschungsgemeinschaft
  • Fonds der Chemischen Industrie

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Keywords:

  • Hafnium;
  • Zirconium;
  • Titanium;
  • Oligomerization;
  • Polymerization;
  • Regioselectivity

Abstract

Reaction of group 4 metal tetrabenzyl complexes [M(CH2Ph)4] (M = Ti, Zr, Hf) with 1 or 2 equiv. of a thioether-functionalized phenol 2,4-tBu2-6-(PhSCH2)C6H2OH afforded dibenzyl complexes [M(L)2(CH2Ph)2] (M = Ti, 1; M = Zr, 2; M = Hf, 3) and the tribenzyl zirconium complex [Zr(L)(CH2Ph)3] (4). Benzyl abstraction with a Lewis acid gave the zirconium monobenzyl cation [Zr(L)2CH2Ph]+[PhCH2B(C6F5)3]– (5) and the dibenzyl cation [Zr(L)(CH2Ph)2]+[PhCH2B(C6F5)3]– (6). The monobenzyl cation 5 oligomerized 1-hexene to low molecular-weight atactic oligo(1-hexene) (Mn = 560–820), while the dibenzyl cation 6 polymerized 1-hexene isospecifically ([mmmm] > 90 %). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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