Effect of Al Cocatalyst in Ethylene and Ethylene/Norbornene (Co)polymerization by (Imido)vanadium Dichloride Complexes Containing Anionic <i>N</i>-Heterocyclic Carbenes Having Weakly Coordinating Borate Moiety

Abstract

Effect of Al cocatalyst in ethylene polymerization using (imido)vanadium(V) complexes containing anionic N-heterocyclic carbenes with a weakly coordinating borate moiety in 4-position (WCA-NHC), [V(N-2,6-Me2C6H3)Cl2(WCA-NHC)] [1; NHC=1,3-bis(2,6-dimethylphenyl)-imidazolin-2-ylidene], have been explored. The activities by 1 upon presence of AliBu3 in ethylene polymerization and in the copolymerization with norbornene (NBE) were higher than those in the presence of MAO, and the resultant poly(ethylene-co-NBE)s prepared by 1-AliBu3 catalyst possessed uniform molecular weight distributions and compositions. Formation of vanadium(III) species could be assumed upon presence of AliBu3, especially on the basis of both NMR and ESR spectra (silent) and certain significant changes in the V K-edge XANES (pre-edge and edge region) spectrum, whereas no significant changes in the XANES spectrum were observed from the toluene solution containing 1 upon addition of MAO. It is thus suggested that a difference in the catalyst performances between in the presence of MAO and AliBu3 should be due to a formation of different catalytically active species with different oxidation states.