Vanadium(V) Complexes Containing Unsymmetrical <italic style="font-style: italic">N</italic>-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization

Yi-Cong Wang; Hui Zha; Pei-Yi Cheng; Shu Zhang; Xiang-Wei Liu; Yi-Xian Wu

doi:10.1007/s10118-023-3020-5

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Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization

RESEARCH ARTICLE | Updated：2023-12-26

- Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization
- Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization
- 高分子科学（英文版） 2024年42卷第1期页码：32-41
- Affiliations：
  
  State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
- Author bio：
  
  zhangshu@buct.edu.cn (S.Z.)
  wuyx@buct.edu.cn (Y.X.W.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 21774006 and 21634002).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-023-3020-5.
- DOI：10.1007/s10118-023-3020-5
  中图分类号：
- 收稿：2023-04-07，
  
  修回：2023-6-5，
  
  录用：2023-6-10，
  
  网络首发：2023-08-07，
  
  纸质出版：2024-01-01
- Accepted：
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Wang, Y. C.; Zha, H.; Cheng, P. Y.; Zhang, S.; Liu, X. W.; Wu, Y. X. Vanadium(V) complexes containing unsymmetrical N-heterocyclic carbene ligands: highly efficient synthesis and catalytic behavior towards ethylene/propylene copolymerization. Chinese J. Polym. Sci. 2024, 42, 32–41

Yi-Cong Wang, Hui Zha, Pei-Yi Cheng, et al. Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization[J]. Chinese Journal of Polymer Science, 2024, 42(1): 32-41. DOI: 10.1007/s10118-023-3020-5.
Wang, Y. C.; Zha, H.; Cheng, P. Y.; Zhang, S.; Liu, X. W.; Wu, Y. X. Vanadium(V) complexes containing unsymmetrical N-heterocyclic carbene ligands: highly efficient synthesis and catalytic behavior towards ethylene/propylene copolymerization. Chinese J. Polym. Sci. 2024, 42, 32–41 DOI： 10.1007/s10118-023-3020-5.

Yi-Cong Wang, Hui Zha, Pei-Yi Cheng, et al. Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization[J]. Chinese Journal of Polymer Science, 2024, 42(1): 32-41. DOI: 10.1007/s10118-023-3020-5. DOI：

摘要

The highly efficient method has been developed for the synthesis of NHC·VOCl3 containing unsymmetrical N-heterocyclic carbene (NHC) ligands

which show high catalytic activity and good copolymerization ability toward ethylene/propylene copolymerization.

Abstract

The highly efficient method has been developed for the synthesis of NHC·VOCl

containing symmetrical or unsymmetrical

-heterocyclic carbene (NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl

. The total isolated yield of VOCl

3-(2

6-Me

)

(NCH=)

C:] (

V4'

) reached 86% by transmetallation reaction

which is much higher than that (48%) by direct coordination method. This methodology has also been used to synthesize the novel vanadium complexes containing unsymmetrical NHC ligands of VOCl

[PhCH

NCH=CHNR)C:] (

V5’

R = 2

6-Me

;

V6’

R = 2

4-Me

-6-Ph-C

;

V7’

R = 2

-C

) with high yield

which could not be obtained by direct coordination method. The catalytic activity and copolymerization ability would be improved by introducing unsymmetrical NHC ligands due to their less steric bulky effect. The vanadium complex

V5’

containing unsymmetrical NHC ligand exhibits higher catalytic activity (3.7×10

copolymer

·mol

−1

of V·h

−1

) than that of

V4'

containing symmetrical NHC ligand. Moreover

the higher propylene incorporation ratio (45.6 mol%) in the copolymers of ethylene with propylene could be obtained by using

V5’

than that (39.9%) by using

V4'

. The results would provide a highly efficient strategy for the synthesis of early transition metal complexes containing versitile NHC ligands

affording the catalyst with both high catalytic activity and copolymerization ability for the synthesis of high performance polyolefin elastomers.

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references

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Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization

DOI：10.1007/s10118-023-3020-5

摘要

Abstract

关键词

Keywords

references