Vanadium(v) arylimido alkylidene N-heterocyclic carbene complexes containing fluorinated alkoxide or halogenated phenoxide ligands for the syndiospecific ROMP of cyclic olefins
[V(N-2,6-Cl2C6H3)(CHSiMe3)(OC6X5)(NHC)] [X = F (1), Cl (2), NHC = 1,3-bis-(2,6-dimethylphenyl)-imidazol-2-ylidene], exhibited remarkable catalytic activities [TOF = 133–193 s−1 (1), 90.9–126 s−1 (2)] for ring opening metathesis polymerisation (ROMP) of norbornene (NBE) at 25 °C to afford ring-opened polymers not only with high cis-(93–98%) selectivity, but also with exclusive syndiotactic stereo-regularity. These polymerisations proceeded in a living manner under optimised conditions. The activity improved at 50 °C with decreasing in the cis specificity. Synthesis and the structural analysis of the fluorinated alkoxide complexes, [V(N-2,6-X2C6H3)(CHSiMe3)OC(CF3)3(NHC)] [X = F (3), Cl (4)] have been studied, and the difluorophenylimdo complex (3) exhibited comparable catalytic activities for ROMP of NBE. The cis selectivities in the resultant polymers prepared by 3 were low (88%) and the selectivities in the ring-opened poly(tetracyclododecene) (TCD) were low (61–66%) compared to those in poly(NBE)s. The resultant ring opened poly(TCD) possessed syndiotactic stereo-regularity confirmed by DSC thermogram of the hydrogenated polymers.
%0 Journal Article
%1 D4NJ02537G
%A Nomura, Kotohiro
%A Kuwahara, Shuko
%A Suthala, Jirapa
%A Kawamoto, Yuta
%A Shimoyama, Daisuke
%A Buchmeiser, Michael R.
%D 2024
%I The Royal Society of Chemistry
%J New J. Chem.
%K 2024.12.13
%N 34
%P 14865-14872
%R 10.1039/D4NJ02537G
%T Vanadium(v) arylimido alkylidene N-heterocyclic carbene complexes containing fluorinated alkoxide or halogenated phenoxide ligands for the syndiospecific ROMP of cyclic olefins
%U http://dx.doi.org/10.1039/D4NJ02537G
%V 48
%X [V(N-2,6-Cl2C6H3)(CHSiMe3)(OC6X5)(NHC)] [X = F (1), Cl (2), NHC = 1,3-bis-(2,6-dimethylphenyl)-imidazol-2-ylidene], exhibited remarkable catalytic activities [TOF = 133–193 s−1 (1), 90.9–126 s−1 (2)] for ring opening metathesis polymerisation (ROMP) of norbornene (NBE) at 25 °C to afford ring-opened polymers not only with high cis-(93–98%) selectivity, but also with exclusive syndiotactic stereo-regularity. These polymerisations proceeded in a living manner under optimised conditions. The activity improved at 50 °C with decreasing in the cis specificity. Synthesis and the structural analysis of the fluorinated alkoxide complexes, [V(N-2,6-X2C6H3)(CHSiMe3)OC(CF3)3(NHC)] [X = F (3), Cl (4)] have been studied, and the difluorophenylimdo complex (3) exhibited comparable catalytic activities for ROMP of NBE. The cis selectivities in the resultant polymers prepared by 3 were low (88%) and the selectivities in the ring-opened poly(tetracyclododecene) (TCD) were low (61–66%) compared to those in poly(NBE)s. The resultant ring opened poly(TCD) possessed syndiotactic stereo-regularity confirmed by DSC thermogram of the hydrogenated polymers.
@article{D4NJ02537G,
abstract = {[V(N-2{,}6-Cl2C6H3)(CHSiMe3)(OC6X5)(NHC)] [X = F (1){,} Cl (2){,} NHC = 1{,}3-bis-(2{,}6-dimethylphenyl)-imidazol-2-ylidene]{,} exhibited remarkable catalytic activities [TOF = 133–193 s−1 (1){,} 90.9–126 s−1 (2)] for ring opening metathesis polymerisation (ROMP) of norbornene (NBE) at 25 °C to afford ring-opened polymers not only with high cis-(93–98%) selectivity{,} but also with exclusive syndiotactic stereo-regularity. These polymerisations proceeded in a living manner under optimised conditions. The activity improved at 50 °C with decreasing in the cis specificity. Synthesis and the structural analysis of the fluorinated alkoxide complexes{,} [V(N-2{,}6-X2C6H3)(CHSiMe3){OC(CF3)3}(NHC)] [X = F (3){,} Cl (4)] have been studied{,} and the difluorophenylimdo complex (3) exhibited comparable catalytic activities for ROMP of NBE. The cis selectivities in the resultant polymers prepared by 3 were low (88%) and the selectivities in the ring-opened poly(tetracyclododecene) (TCD) were low (61–66%) compared to those in poly(NBE)s. The resultant ring opened poly(TCD) possessed syndiotactic stereo-regularity confirmed by DSC thermogram of the hydrogenated polymers.},
added-at = {2024-12-16T14:09:39.000+0100},
author = {Nomura, Kotohiro and Kuwahara, Shuko and Suthala, Jirapa and Kawamoto, Yuta and Shimoyama, Daisuke and Buchmeiser, Michael R.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2214cd347a42d3aca7ceccbb96a785aec/dwang},
doi = {10.1039/D4NJ02537G},
interhash = {14e85586a9db3a267ea6c19f0c28a19c},
intrahash = {214cd347a42d3aca7ceccbb96a785aec},
journal = {New J. Chem.},
keywords = {2024.12.13},
number = 34,
pages = {14865-14872},
publisher = {The Royal Society of Chemistry},
timestamp = {2024-12-16T14:13:01.000+0100},
title = {Vanadium(v) arylimido alkylidene N-heterocyclic carbene complexes containing fluorinated alkoxide or halogenated phenoxide ligands for the syndiospecific ROMP of cyclic olefins},
url = {http://dx.doi.org/10.1039/D4NJ02537G},
volume = 48,
year = 2024
}