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.