High-temperature single-site ethylene polymerization behavior of titanate complexes supported by 1,3-bis(3,5-dialkylpyrazol-1-yl)propan-2-olate ligation

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Abstract

Titanate(1-) complexes Na[(THF)(κ1-O-bdbpzp)TiCl 4] (1) and Na[(THF)(κ1-O-bdmpzp)TiCl4] (2) and titanate(2-) complexes [Na(THF)]2[(κ1-O- bdbpzp)2TiCl4] (4) and [Na(THF)]2[(κ 1-O-bdmpzp)2TiCl4] (5) were obtained in good yield from reaction of Na[bdbpzp] or Na[bdmpzp] (sodium salt of 1,3-bis(3,5-di-tert-butylpyrazol-1yl)propan-2-ol or 1,3-bis(3,5-dimethylpyrazol- 1yl)propan-2-ol) with TiCl4 (in the appropriate molar ratio) at 0-25°C. Protonolysis of TiCl4 with 1 equiv of bdmpzpH furnished related zwitterionic titanate(1-) complex 3 that possessed a κ2-N,O-coordinated pyrazolyl-alkoxide with pendant pyrazolium group. Methylalumoxane (MAO) activation of 1-5 under high-temperature solution polymerization conditions produced active single-site ethylene polymerization catalysts that exhibit considerably higher thermal stability (especially 2/MAO, 3/MAO, and 5/MAO) than previously reported for Cp2TiCl 2/MAO or Ti catalysts supported by related heteroscorpionate or scorpionate ligation.

Original languageEnglish
Pages (from-to)9495-9502
Number of pages8
JournalInorganic Chemistry
Volume46
Issue number22
DOIs
StatePublished - Oct 29 2007

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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