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

作　　者：Kotohiro Nomura Sapanna Chaimongkolkunasin 

机构地区：[1]Department of Chemistry Graduate School of Science, Tokyo Metropolitan University

出　　处：《Chinese Journal of Polymer Science》2019年第10期943-950,I0002,共9页高分子科学（英文版）

基　　金：partly supported by Grant-in-Aid for Scientific Research on Innovative Areas ("3D Active-Site Science", No. 26105003) from The Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan;Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (JSPS, Nos. 15H03812, 18H01982);the Tokyo Metropolitan government (Tokyo Human Resources Fund for City Diplomacy) for pre-doctoral fellowship

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)].(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 °C. 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 × 104 min–1（upon addition of C6F5OH） versus 37.3 min–1（none）].

关 键 词：OLEFIN METATHESIS Molecular CATALYST RING-OPENING METATHESIS polymerization Cyclic OLEFIN VANADIUM CATALYST 

分 类 号：O62[理学—有机化学]