(Arylimido)vanadium(V)-Alkylidene Complexes as Catalysts for Ring-opening Metathesis Polymerization(ROMP) of Cyclic Olefins: Ligand Design for Exhibiting the High Activity

摘要

(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalytic activities for ringopening metathesis polymerization(ROMP) of norbornene(NBE). The catalytic activities were affected by the ligand substituents, and V(CHSiMe3)(N-2,6-Cl2C6H3)(OC6X5)(PMe3)2(X = F, Cl) demonstrated the exceptionally high catalytic activities for ROMP of NBE.The complexes polymerized cycloheptene(CHPE) and cis-cyclooctene(COE), and ROMP of COE by the OC6 Cl5 analogue proceeded in a living manner even at 80℃, and the activity increased with increasing the temperature up to 120 ℃. Highly active catalysts for ROMP of cyclic olefins(NBE, cyclopentene, and CHPE) can be generated in situ by premixing isolated V(CHSiMe3)(NC6F5)(O-2,6-iPr2C6H3)(PMe3)2 with 1.0 equiv. of C6F5OH or C6Cl5OH via immediate phenoxy exchange;the activity was affected by the kind of phenol added [TOF in the ROMPs of NBE: 4.62 × 10^4 min^–1(upon addition of C6F5OH) versus 37.3 min^–1(none)].