

FOLLOWUS
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
zhangshu@buct.edu.cn (S.Z.)
wuyx@buct.edu.cn (Y.X.W.)
Received:07 April 2023,
Revised:2023-6-5,
Accepted:10 June 2023,
Online First:07 August 2023,
Published:01 January 2024
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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
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
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.
The highly efficient method has been developed for the synthesis of NHC·VOCl
3
containing symmetrical or unsymmetrical
N
-heterocyclic carbene (NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl
3
. The total isolated yield of VOCl
3
[1
3-(2
4
6-Me
3
C
6
H
2
)
2
(NCH=)
2
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
3
[PhCH
2
NCH=CHNR)C:] (
V5’
R = 2
4
6-Me
3
C
6
H
2
;
V6’
R = 2
4-Me
2
-6-Ph-C
6
H
2
;
V7’
R = 2
6-
i
Pr
2
-C
6
H
3
) 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
5
g
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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