Polymer-free ethylene oligomerization using a pyridine-based pincer PNP-type of ligand

Ahmed Alzamly; Sandro Gambarotta; Ilia Korobkov

doi:10.1021/om4008828

Polymer-free ethylene oligomerization using a pyridine-based pincer PNP-type of ligand

Ahmed Alzamly, Sandro Gambarotta, Ilia Korobkov

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38 Citations (Scopus)

Abstract

Di- and trivalent chromium complexes of the pyridine-based ligand [2,6-(Ph₂PCH₂)₂ C₅H ₃N]CrCl₃ (1) and {[2,6-(Ph₂CH₂) ₂C₅H₃N]CrCl₂}.(THF) (2) and their aluminate aggregates [2,6-(Ph₂CH₂)₂C ₅H₃NCrCl(μ-Cl)AlClMe₂] (3), {[(2,6-(Ph ₂CH₂)₂C₅H₃NCrCl(μ-Cl) AlClEt₂]}. (toluene)_0.5 (4), {2,6-(Ph₂CH ₂)₂C₅H₃NCrEt(μ-Cl) ₂AlEt₂}{AlCl₃Et} (5), {2,6-(PPh ₂CH₂) C₅H₃N (PPh₂CH)Al(i- Bu)₂(μ-Cl)Cr(μ-Cl)₂Al(i-Bu)₂}.(toluene) _1.5 (6), and {[2,6-(PPh₂CH₂)₂C ₅H₃ N]₂Cr} {(μ-Cl)[Al(i-Bu) ₃]₂} (7) were prepared, isolated, and their activities toward ethylene oligomerization tested. While complexes 3, 5, and 6 were directly accessible by reacting catalyst precursor 1 with Me₃Al, DEAC, and TIBA, respectively, complexes 4 and 7 were prepared using catalyst precursor 2 with DEAC and TIBA, respectively. All these complexes, with the exception of 7, showed good activities for a polymer-free ethylene oligomerization. Complex 7 contains cationic chromium in its monovalent state and its encapsulation in an octahedral ligand field as defined by two ligands is probably responsible for its failure as a catalyst.

Original language	English
Pages (from-to)	7204-7212
Number of pages	9
Journal	Organometallics
Volume	32
Issue number	23
DOIs	https://doi.org/10.1021/om4008828
Publication status	Published - Dec 9 2013
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om4008828

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@article{c15f5a7fdc524bb5b71237b1992f26c4,

title = "Polymer-free ethylene oligomerization using a pyridine-based pincer PNP-type of ligand",

abstract = "Di- and trivalent chromium complexes of the pyridine-based ligand [2,6-(Ph2PCH2)2 C5H 3N]CrCl3 (1) and {[2,6-(Ph2CH2) 2C5H3N]CrCl2}.(THF) (2) and their aluminate aggregates [2,6-(Ph2CH2)2C 5H3NCrCl(μ-Cl)AlClMe2] (3), {[(2,6-(Ph 2CH2)2C5H3NCrCl(μ-Cl) AlClEt2]}. (toluene)0.5 (4), {2,6-(Ph2CH 2)2C5H3NCrEt(μ-Cl) 2AlEt2}{AlCl3Et} (5), {2,6-(PPh 2CH2) C5H3N (PPh2CH)Al(i- Bu)2(μ-Cl)Cr(μ-Cl)2Al(i-Bu)2}.(toluene) 1.5 (6), and {[2,6-(PPh2CH2)2C 5H3 N]2Cr} {(μ-Cl)[Al(i-Bu) 3]2} (7) were prepared, isolated, and their activities toward ethylene oligomerization tested. While complexes 3, 5, and 6 were directly accessible by reacting catalyst precursor 1 with Me3Al, DEAC, and TIBA, respectively, complexes 4 and 7 were prepared using catalyst precursor 2 with DEAC and TIBA, respectively. All these complexes, with the exception of 7, showed good activities for a polymer-free ethylene oligomerization. Complex 7 contains cationic chromium in its monovalent state and its encapsulation in an octahedral ligand field as defined by two ligands is probably responsible for its failure as a catalyst.",

author = "Ahmed Alzamly and Sandro Gambarotta and Ilia Korobkov",

year = "2013",

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doi = "10.1021/om4008828",

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T1 - Polymer-free ethylene oligomerization using a pyridine-based pincer PNP-type of ligand

AU - Alzamly, Ahmed

AU - Gambarotta, Sandro

AU - Korobkov, Ilia

PY - 2013/12/9

Y1 - 2013/12/9

N2 - Di- and trivalent chromium complexes of the pyridine-based ligand [2,6-(Ph2PCH2)2 C5H 3N]CrCl3 (1) and {[2,6-(Ph2CH2) 2C5H3N]CrCl2}.(THF) (2) and their aluminate aggregates [2,6-(Ph2CH2)2C 5H3NCrCl(μ-Cl)AlClMe2] (3), {[(2,6-(Ph 2CH2)2C5H3NCrCl(μ-Cl) AlClEt2]}. (toluene)0.5 (4), {2,6-(Ph2CH 2)2C5H3NCrEt(μ-Cl) 2AlEt2}{AlCl3Et} (5), {2,6-(PPh 2CH2) C5H3N (PPh2CH)Al(i- Bu)2(μ-Cl)Cr(μ-Cl)2Al(i-Bu)2}.(toluene) 1.5 (6), and {[2,6-(PPh2CH2)2C 5H3 N]2Cr} {(μ-Cl)[Al(i-Bu) 3]2} (7) were prepared, isolated, and their activities toward ethylene oligomerization tested. While complexes 3, 5, and 6 were directly accessible by reacting catalyst precursor 1 with Me3Al, DEAC, and TIBA, respectively, complexes 4 and 7 were prepared using catalyst precursor 2 with DEAC and TIBA, respectively. All these complexes, with the exception of 7, showed good activities for a polymer-free ethylene oligomerization. Complex 7 contains cationic chromium in its monovalent state and its encapsulation in an octahedral ligand field as defined by two ligands is probably responsible for its failure as a catalyst.

AB - Di- and trivalent chromium complexes of the pyridine-based ligand [2,6-(Ph2PCH2)2 C5H 3N]CrCl3 (1) and {[2,6-(Ph2CH2) 2C5H3N]CrCl2}.(THF) (2) and their aluminate aggregates [2,6-(Ph2CH2)2C 5H3NCrCl(μ-Cl)AlClMe2] (3), {[(2,6-(Ph 2CH2)2C5H3NCrCl(μ-Cl) AlClEt2]}. (toluene)0.5 (4), {2,6-(Ph2CH 2)2C5H3NCrEt(μ-Cl) 2AlEt2}{AlCl3Et} (5), {2,6-(PPh 2CH2) C5H3N (PPh2CH)Al(i- Bu)2(μ-Cl)Cr(μ-Cl)2Al(i-Bu)2}.(toluene) 1.5 (6), and {[2,6-(PPh2CH2)2C 5H3 N]2Cr} {(μ-Cl)[Al(i-Bu) 3]2} (7) were prepared, isolated, and their activities toward ethylene oligomerization tested. While complexes 3, 5, and 6 were directly accessible by reacting catalyst precursor 1 with Me3Al, DEAC, and TIBA, respectively, complexes 4 and 7 were prepared using catalyst precursor 2 with DEAC and TIBA, respectively. All these complexes, with the exception of 7, showed good activities for a polymer-free ethylene oligomerization. Complex 7 contains cationic chromium in its monovalent state and its encapsulation in an octahedral ligand field as defined by two ligands is probably responsible for its failure as a catalyst.

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DO - 10.1021/om4008828

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JO - Organometallics

JF - Organometallics

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ER -

Polymer-free ethylene oligomerization using a pyridine-based pincer PNP-type of ligand

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