Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands

Fábio A. Kunrath; Roberto F. De Souza; Osvaldo L. Casagrande; Neil R. Brooks; Victor G. Young

doi:10.1021/om034035u

Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands

Fábio A. Kunrath, Roberto F. De Souza, Osvaldo L. Casagrande, Neil R. Brooks, Victor G. Young

Chemistry (Twin Cities)

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

100 Scopus citations

Abstract

The reaction of TlTp′ (Tp′ = HB(3-mesitylpyrazolyl)₃^- (Tp^Ms), HB(3-mesitylpyrazolyl)₂(5-mesitylpyrazolyl)^- (Tp^Ms*)) with NiCl₂·6H₂O affords Tp^MsNiCl (1) and Tp^Ms*NiCl (2) in good yield. The compound 2 undergoes an isomerization process to form [{Tp^Ms**}NiCl]₂ (3) (Tp^Ms**= HB(5-mesitylpyrazolyl)₂(3-mesitylpyrazolyl)^-) in 68% yield. Treatment of the tris(pyrazolyl)-borate nickel compounds 1 and 2 with alkylaluminum cocatalysts such as methylalumoxane (MAO) and trimethylaluminum (TMA) in toluene generates active catalysts for ethylene oligomerization. The compound 1 shows turnover frequencies in the range of (2.2 - 43.1) × 10³ h^-1. Oligomerization reaction conditions can be adjusted that lead to selectivities as high as 81% for butene-1.

Original language	English (US)
Pages (from-to)	4739-4743
Number of pages	5
Journal	Organometallics
Volume	22
Issue number	23
DOIs	https://doi.org/10.1021/om034035u
State	Published - Nov 10 2003

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title = "Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands",

abstract = "The reaction of TlTp′ (Tp′ = HB(3-mesitylpyrazolyl)3- (TpMs), HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)- (TpMs*)) with NiCl2·6H2O affords TpMsNiCl (1) and TpMs*NiCl (2) in good yield. The compound 2 undergoes an isomerization process to form [{TpMs**}NiCl]2 (3) (TpMs**= HB(5-mesitylpyrazolyl)2(3-mesitylpyrazolyl)-) in 68% yield. Treatment of the tris(pyrazolyl)-borate nickel compounds 1 and 2 with alkylaluminum cocatalysts such as methylalumoxane (MAO) and trimethylaluminum (TMA) in toluene generates active catalysts for ethylene oligomerization. The compound 1 shows turnover frequencies in the range of (2.2 - 43.1) × 103 h-1. Oligomerization reaction conditions can be adjusted that lead to selectivities as high as 81% for butene-1.",

author = "Kunrath, {F{\'a}bio A.} and {De Souza}, {Roberto F.} and Casagrande, {Osvaldo L.} and Brooks, {Neil R.} and Young, {Victor G.}",

year = "2003",

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language = "English (US)",

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T1 - Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands

AU - Kunrath, Fábio A.

AU - De Souza, Roberto F.

AU - Casagrande, Osvaldo L.

AU - Brooks, Neil R.

AU - Young, Victor G.

PY - 2003/11/10

Y1 - 2003/11/10

N2 - The reaction of TlTp′ (Tp′ = HB(3-mesitylpyrazolyl)3- (TpMs), HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)- (TpMs*)) with NiCl2·6H2O affords TpMsNiCl (1) and TpMs*NiCl (2) in good yield. The compound 2 undergoes an isomerization process to form [{TpMs**}NiCl]2 (3) (TpMs**= HB(5-mesitylpyrazolyl)2(3-mesitylpyrazolyl)-) in 68% yield. Treatment of the tris(pyrazolyl)-borate nickel compounds 1 and 2 with alkylaluminum cocatalysts such as methylalumoxane (MAO) and trimethylaluminum (TMA) in toluene generates active catalysts for ethylene oligomerization. The compound 1 shows turnover frequencies in the range of (2.2 - 43.1) × 103 h-1. Oligomerization reaction conditions can be adjusted that lead to selectivities as high as 81% for butene-1.

AB - The reaction of TlTp′ (Tp′ = HB(3-mesitylpyrazolyl)3- (TpMs), HB(3-mesitylpyrazolyl)2(5-mesitylpyrazolyl)- (TpMs*)) with NiCl2·6H2O affords TpMsNiCl (1) and TpMs*NiCl (2) in good yield. The compound 2 undergoes an isomerization process to form [{TpMs**}NiCl]2 (3) (TpMs**= HB(5-mesitylpyrazolyl)2(3-mesitylpyrazolyl)-) in 68% yield. Treatment of the tris(pyrazolyl)-borate nickel compounds 1 and 2 with alkylaluminum cocatalysts such as methylalumoxane (MAO) and trimethylaluminum (TMA) in toluene generates active catalysts for ethylene oligomerization. The compound 1 shows turnover frequencies in the range of (2.2 - 43.1) × 103 h-1. Oligomerization reaction conditions can be adjusted that lead to selectivities as high as 81% for butene-1.

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Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands

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