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

Richard Eaves; Sean Parkin; Folami T. Ladipo

doi:10.1021/ic701221f

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

Richard Eaves, Sean Parkin, Folami T. Ladipo

Chemistry

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

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 language	English
Pages (from-to)	9495-9502
Number of pages	8
Journal	Inorganic Chemistry
Volume	46
Issue number	22
DOIs	https://doi.org/10.1021/ic701221f
State	Published - Oct 29 2007

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{47feda00f95349fdbeee78c42461c559,

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

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.",

author = "Richard Eaves and Sean Parkin and Ladipo, {Folami T.}",

year = "2007",

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T1 - High-temperature single-site ethylene polymerization behavior of titanate complexes supported by 1,3-bis(3,5-dialkylpyrazol-1-yl)propan-2-olate ligation

AU - Eaves, Richard

AU - Parkin, Sean

AU - Ladipo, Folami T.

PY - 2007/10/29

Y1 - 2007/10/29

N2 - 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.

AB - 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.

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SN - 0020-1669

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

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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