Cobalt complexes bearing pyridine-imino ligands with bulky aryl substituents: Synthesis, characterization, and 1,3-butadiene polymerization behaviors

Jun Guo; Chunyu Zhang; Jifu Bi; Hexin Zhang; Chenxi Bai; Yanming Hu; Xuequan Zhang

doi:10.1016/j.jorganchem.2015.05.004

Cobalt complexes bearing pyridine-imino ligands with bulky aryl substituents: Synthesis, characterization, and 1,3-butadiene polymerization behaviors

Jun Guo, Chunyu Zhang, Jifu Bi, Hexin Zhang, Chenxi Bai, Yanming Hu, Xuequan Zhang

Chemical Engineering and Materials Science

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

9 Scopus citations

Abstract

A series of Co(II) complexes bearing pyridine-imino ligands [2-Ar₁-6-(CMe = NAr₂)C₅H₃N]CoCl₂ (Ar₁ = C₆H₅, Ar₂ = 2,6-i-Pr₂C₆H₃ (3a); Ar₁ = 2′-C₁₀H₇, Ar₂ = 2,6-i-Pr₂C₆H₃ (3b); Ar₁ = 2′-C₁₀H₇, Ar₂ = C₆H₅ (3c); Ar₁ = 2′-C₁₀H₇, Ar₂ = 4-ClC₆H₄ (3d); Ar₁ = 4′-C₆H₅-C₆H₄, Ar₂ = 2,6-i-Pr₂C₆H₃ (3e); Ar₁ = 4′-C₆H₅-C₆H₄, Ar₂ = C₆H₅ (3f); Ar₁ = 4′-C₆H₅-C₆H₄, Ar₂ = 4-ClC₆H₄ (3g)) with bulky aryl groups were synthesized and characterized. Determined by single-crystal X-ray diffraction, 3a, 3b, and 3e adopted distorted tetrahedron configurations. Activated by ethylaluminum sesquichloride (EASC), these complexes exhibited high cis-1,4 selectivity for 1,3-butadiene polymerization. The steric and electronic properties of substituent of the ligand remarkably influenced catalytic activity. The effects of polymerization parameters such as [Al]/[Co] ratio and temperature on the polymerization were also investigated in details.

Original language	English (US)
Pages (from-to)	414-421
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	798
DOIs	https://doi.org/10.1016/j.jorganchem.2015.05.004
State	Published - Dec 1 2015

Bibliographical note

Funding Information:
The authors appreciate financial support from National Basic Research Program of China , Grant No. 2015CB654700 ( 2015CB674702 ), The CAS Hundred Talents Program ( Y220011001 ), the Fund for National Natural Scientific Foundation of China (No. 51473156 ), National Natural Scientific Foundation of China (No. 51203147 ) and Jilin Provincial Research Fund for Basic Research, China (No. 20130102007JC ).

Publisher Copyright:
© 2015 Elsevier B.V.

Keywords

1,3-Butadiene polymerization
Cobalt complex
Pyridine-imino ligand

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10.1016/j.jorganchem.2015.05.004

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@article{eac4d5dd740c49409f542ef64bbef4ea,

title = "Cobalt complexes bearing pyridine-imino ligands with bulky aryl substituents: Synthesis, characterization, and 1,3-butadiene polymerization behaviors",

abstract = "A series of Co(II) complexes bearing pyridine-imino ligands [2-Ar1-6-(CMe = NAr2)C5H3N]CoCl2 (Ar1 = C6H5, Ar2 = 2,6-i-Pr2C6H3 (3a); Ar1 = 2′-C10H7, Ar2 = 2,6-i-Pr2C6H3 (3b); Ar1 = 2′-C10H7, Ar2 = C6H5 (3c); Ar1 = 2′-C10H7, Ar2 = 4-ClC6H4 (3d); Ar1 = 4′-C6H5-C6H4, Ar2 = 2,6-i-Pr2C6H3 (3e); Ar1 = 4′-C6H5-C6H4, Ar2 = C6H5 (3f); Ar1 = 4′-C6H5-C6H4, Ar2 = 4-ClC6H4 (3g)) with bulky aryl groups were synthesized and characterized. Determined by single-crystal X-ray diffraction, 3a, 3b, and 3e adopted distorted tetrahedron configurations. Activated by ethylaluminum sesquichloride (EASC), these complexes exhibited high cis-1,4 selectivity for 1,3-butadiene polymerization. The steric and electronic properties of substituent of the ligand remarkably influenced catalytic activity. The effects of polymerization parameters such as [Al]/[Co] ratio and temperature on the polymerization were also investigated in details.",

keywords = "1,3-Butadiene polymerization, Cobalt complex, Pyridine-imino ligand",

author = "Jun Guo and Chunyu Zhang and Jifu Bi and Hexin Zhang and Chenxi Bai and Yanming Hu and Xuequan Zhang",

note = "Funding Information: The authors appreciate financial support from National Basic Research Program of China , Grant No. 2015CB654700 ( 2015CB674702 ), The CAS Hundred Talents Program ( Y220011001 ), the Fund for National Natural Scientific Foundation of China (No. 51473156 ), National Natural Scientific Foundation of China (No. 51203147 ) and Jilin Provincial Research Fund for Basic Research, China (No. 20130102007JC ). Publisher Copyright: {\textcopyright} 2015 Elsevier B.V.",

year = "2015",

month = dec,

day = "1",

doi = "10.1016/j.jorganchem.2015.05.004",

language = "English (US)",

volume = "798",

pages = "414--421",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

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TY - JOUR

T1 - Cobalt complexes bearing pyridine-imino ligands with bulky aryl substituents

T2 - Synthesis, characterization, and 1,3-butadiene polymerization behaviors

AU - Guo, Jun

AU - Zhang, Chunyu

AU - Bi, Jifu

AU - Zhang, Hexin

AU - Bai, Chenxi

AU - Hu, Yanming

AU - Zhang, Xuequan

N1 - Funding Information: The authors appreciate financial support from National Basic Research Program of China , Grant No. 2015CB654700 ( 2015CB674702 ), The CAS Hundred Talents Program ( Y220011001 ), the Fund for National Natural Scientific Foundation of China (No. 51473156 ), National Natural Scientific Foundation of China (No. 51203147 ) and Jilin Provincial Research Fund for Basic Research, China (No. 20130102007JC ). Publisher Copyright: © 2015 Elsevier B.V.

PY - 2015/12/1

Y1 - 2015/12/1

N2 - A series of Co(II) complexes bearing pyridine-imino ligands [2-Ar1-6-(CMe = NAr2)C5H3N]CoCl2 (Ar1 = C6H5, Ar2 = 2,6-i-Pr2C6H3 (3a); Ar1 = 2′-C10H7, Ar2 = 2,6-i-Pr2C6H3 (3b); Ar1 = 2′-C10H7, Ar2 = C6H5 (3c); Ar1 = 2′-C10H7, Ar2 = 4-ClC6H4 (3d); Ar1 = 4′-C6H5-C6H4, Ar2 = 2,6-i-Pr2C6H3 (3e); Ar1 = 4′-C6H5-C6H4, Ar2 = C6H5 (3f); Ar1 = 4′-C6H5-C6H4, Ar2 = 4-ClC6H4 (3g)) with bulky aryl groups were synthesized and characterized. Determined by single-crystal X-ray diffraction, 3a, 3b, and 3e adopted distorted tetrahedron configurations. Activated by ethylaluminum sesquichloride (EASC), these complexes exhibited high cis-1,4 selectivity for 1,3-butadiene polymerization. The steric and electronic properties of substituent of the ligand remarkably influenced catalytic activity. The effects of polymerization parameters such as [Al]/[Co] ratio and temperature on the polymerization were also investigated in details.

AB - A series of Co(II) complexes bearing pyridine-imino ligands [2-Ar1-6-(CMe = NAr2)C5H3N]CoCl2 (Ar1 = C6H5, Ar2 = 2,6-i-Pr2C6H3 (3a); Ar1 = 2′-C10H7, Ar2 = 2,6-i-Pr2C6H3 (3b); Ar1 = 2′-C10H7, Ar2 = C6H5 (3c); Ar1 = 2′-C10H7, Ar2 = 4-ClC6H4 (3d); Ar1 = 4′-C6H5-C6H4, Ar2 = 2,6-i-Pr2C6H3 (3e); Ar1 = 4′-C6H5-C6H4, Ar2 = C6H5 (3f); Ar1 = 4′-C6H5-C6H4, Ar2 = 4-ClC6H4 (3g)) with bulky aryl groups were synthesized and characterized. Determined by single-crystal X-ray diffraction, 3a, 3b, and 3e adopted distorted tetrahedron configurations. Activated by ethylaluminum sesquichloride (EASC), these complexes exhibited high cis-1,4 selectivity for 1,3-butadiene polymerization. The steric and electronic properties of substituent of the ligand remarkably influenced catalytic activity. The effects of polymerization parameters such as [Al]/[Co] ratio and temperature on the polymerization were also investigated in details.

KW - 1,3-Butadiene polymerization

KW - Cobalt complex

KW - Pyridine-imino ligand

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U2 - 10.1016/j.jorganchem.2015.05.004

DO - 10.1016/j.jorganchem.2015.05.004

M3 - Article

AN - SCOPUS:84949624648

SN - 0022-328X

VL - 798

SP - 414

EP - 421

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Cobalt complexes bearing pyridine-imino ligands with bulky aryl substituents: Synthesis, characterization, and 1,3-butadiene polymerization behaviors

Abstract

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