Tantalum complexes incorporating tris(pyrazolyl)borate ligands

Syntheses, structures, and ethylene polymerization behavior

Kenji Michiue, Toshiyuki Oshiki, Kazuhiko Takai, Makoto Mitani, Terunori Fujita

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Four new Ta complexes bearing tris(pyrazolyl)borate ligands, Tp*TaCl(η2-3-hexyne)(benzyl) [1; Tp* = HB(3,5-dimethylpyrazolyl)3-], TpMs* TaCl22-3-hexyne) [2; TpMs* = HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)-], Tp Ms* TaCl2(=N-2,6-i:Pr2C 6H3) (3), and TpMsTaCl2(=N- tBu) [4; TpMs = HB(3-mesitylpyrazolyl)3 ], were prepared in moderate to high yields from appropriate TaCl3(R) (R; η2-3-hexyne, =N-2,6-tPr2C6H 3, =N-tBu) species and the potassium or thallium salt of the corresponding tris(pyrazolyl)borate ligand. The molecular structures of complexes 3 and 4 established by X-ray analyses snowed that these complexes adopted a distorted octahedral geometry in which the Ta metal is coordinated by three N atoms of the tris(pyrazolyl)borate ligand (facial coordination), two cis-located Cl atoms, and the imido group. In combination with dried methylaluminoxane or iBu3Al/Ph3CB(C 6F5)4, complexes 1-4 were all active for ethylene polymerization and produced low to very high molecular weight, highly linear polyethylenes. In particular, upon activation with iBu 3Al/Ph3CB(C6F5)4, high activities were observed for complexes 3 and 4, which possess the sterically encumbered mesityl-substituted tris(pyrazolyl)borate ligand and the imido group as an auxiliary ligand. The activities, 25.7 kg-PE/mmol-Ta-h (complex 3) and 17.1 kg-PE/ mmol-Ta . h (complex 4), represent some of the highest values reported to date for Ta-based catalysts. These highly active Ta-based catalysts were long-lived and maintained a practically steady ethylene uptake for 30 min at 80 °C.

Original languageEnglish
Pages (from-to)6450-6457
Number of pages8
JournalOrganometallics
Volume28
Issue number22
DOIs
Publication statusPublished - Nov 23 2009

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Tantalum
tantalum
borates
ethylene
polymerization
Polymerization
Ligands
ligands
synthesis
Polyethylenes
Bearings (structural)
catalysts
Atoms
Catalysts
Thallium
thallium
Molecular structure
atoms
polyethylenes
molecular weight

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Tantalum complexes incorporating tris(pyrazolyl)borate ligands : Syntheses, structures, and ethylene polymerization behavior. / Michiue, Kenji; Oshiki, Toshiyuki; Takai, Kazuhiko; Mitani, Makoto; Fujita, Terunori.

In: Organometallics, Vol. 28, No. 22, 23.11.2009, p. 6450-6457.

Research output: Contribution to journalArticle

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abstract = "Four new Ta complexes bearing tris(pyrazolyl)borate ligands, Tp*TaCl(η2-3-hexyne)(benzyl) [1; Tp* = HB(3,5-dimethylpyrazolyl)3-], TpMs* TaCl2(η2-3-hexyne) [2; TpMs* = HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)-], Tp Ms* TaCl2(=N-2,6-i:Pr2C 6H3) (3), and TpMsTaCl2(=N- tBu) [4; TpMs = HB(3-mesitylpyrazolyl)3 ], were prepared in moderate to high yields from appropriate TaCl3(R) (R; η2-3-hexyne, =N-2,6-tPr2C6H 3, =N-tBu) species and the potassium or thallium salt of the corresponding tris(pyrazolyl)borate ligand. The molecular structures of complexes 3 and 4 established by X-ray analyses snowed that these complexes adopted a distorted octahedral geometry in which the Ta metal is coordinated by three N atoms of the tris(pyrazolyl)borate ligand (facial coordination), two cis-located Cl atoms, and the imido group. In combination with dried methylaluminoxane or iBu3Al/Ph3CB(C 6F5)4, complexes 1-4 were all active for ethylene polymerization and produced low to very high molecular weight, highly linear polyethylenes. In particular, upon activation with iBu 3Al/Ph3CB(C6F5)4, high activities were observed for complexes 3 and 4, which possess the sterically encumbered mesityl-substituted tris(pyrazolyl)borate ligand and the imido group as an auxiliary ligand. The activities, 25.7 kg-PE/mmol-Ta-h (complex 3) and 17.1 kg-PE/ mmol-Ta . h (complex 4), represent some of the highest values reported to date for Ta-based catalysts. These highly active Ta-based catalysts were long-lived and maintained a practically steady ethylene uptake for 30 min at 80 °C.",
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AU - Mitani, Makoto

AU - Fujita, Terunori

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N2 - Four new Ta complexes bearing tris(pyrazolyl)borate ligands, Tp*TaCl(η2-3-hexyne)(benzyl) [1; Tp* = HB(3,5-dimethylpyrazolyl)3-], TpMs* TaCl2(η2-3-hexyne) [2; TpMs* = HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)-], Tp Ms* TaCl2(=N-2,6-i:Pr2C 6H3) (3), and TpMsTaCl2(=N- tBu) [4; TpMs = HB(3-mesitylpyrazolyl)3 ], were prepared in moderate to high yields from appropriate TaCl3(R) (R; η2-3-hexyne, =N-2,6-tPr2C6H 3, =N-tBu) species and the potassium or thallium salt of the corresponding tris(pyrazolyl)borate ligand. The molecular structures of complexes 3 and 4 established by X-ray analyses snowed that these complexes adopted a distorted octahedral geometry in which the Ta metal is coordinated by three N atoms of the tris(pyrazolyl)borate ligand (facial coordination), two cis-located Cl atoms, and the imido group. In combination with dried methylaluminoxane or iBu3Al/Ph3CB(C 6F5)4, complexes 1-4 were all active for ethylene polymerization and produced low to very high molecular weight, highly linear polyethylenes. In particular, upon activation with iBu 3Al/Ph3CB(C6F5)4, high activities were observed for complexes 3 and 4, which possess the sterically encumbered mesityl-substituted tris(pyrazolyl)borate ligand and the imido group as an auxiliary ligand. The activities, 25.7 kg-PE/mmol-Ta-h (complex 3) and 17.1 kg-PE/ mmol-Ta . h (complex 4), represent some of the highest values reported to date for Ta-based catalysts. These highly active Ta-based catalysts were long-lived and maintained a practically steady ethylene uptake for 30 min at 80 °C.

AB - Four new Ta complexes bearing tris(pyrazolyl)borate ligands, Tp*TaCl(η2-3-hexyne)(benzyl) [1; Tp* = HB(3,5-dimethylpyrazolyl)3-], TpMs* TaCl2(η2-3-hexyne) [2; TpMs* = HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)-], Tp Ms* TaCl2(=N-2,6-i:Pr2C 6H3) (3), and TpMsTaCl2(=N- tBu) [4; TpMs = HB(3-mesitylpyrazolyl)3 ], were prepared in moderate to high yields from appropriate TaCl3(R) (R; η2-3-hexyne, =N-2,6-tPr2C6H 3, =N-tBu) species and the potassium or thallium salt of the corresponding tris(pyrazolyl)borate ligand. The molecular structures of complexes 3 and 4 established by X-ray analyses snowed that these complexes adopted a distorted octahedral geometry in which the Ta metal is coordinated by three N atoms of the tris(pyrazolyl)borate ligand (facial coordination), two cis-located Cl atoms, and the imido group. In combination with dried methylaluminoxane or iBu3Al/Ph3CB(C 6F5)4, complexes 1-4 were all active for ethylene polymerization and produced low to very high molecular weight, highly linear polyethylenes. In particular, upon activation with iBu 3Al/Ph3CB(C6F5)4, high activities were observed for complexes 3 and 4, which possess the sterically encumbered mesityl-substituted tris(pyrazolyl)borate ligand and the imido group as an auxiliary ligand. The activities, 25.7 kg-PE/mmol-Ta-h (complex 3) and 17.1 kg-PE/ mmol-Ta . h (complex 4), represent some of the highest values reported to date for Ta-based catalysts. These highly active Ta-based catalysts were long-lived and maintained a practically steady ethylene uptake for 30 min at 80 °C.

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