Citation: Kotohiro Nomura, Sapanna Chaimongkolkunasin. (Arylimido)vanadium(V)-Alkylidene Complexes as Catalysts for Ring-opening Metathesis Polymerization (ROMP) of Cyclic Olefins: Ligand Design for Exhibiting the High Activity[J]. Chinese Journal of Polymer Science, ;2019, 37(10): 943-950. doi: 10.1007/s10118-019-2298-9 shu

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

Department of Chemistry Graduate School of Science, Tokyo Metropolitan University, Japan

Corresponding author: Kotohiro Nomura, ktnomura@tmu.ac.jp
Received Date: 5 May 2019
Revised Date: 17 May 2019
Available Online: 28 June 2019

(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe₃)(NR)(ORʹ)(PMe₃)₂ [R = Ad, C₆H₅, 2,6-Me₂C₆H₃, 2,6-Cl₂C₆H₃; Rʹ = 2,6-Me₂C₆H₃, 2,6-ⁱPr₂C₆H₃, 2,6-F₂C₆H₃, C₆F₅, C₆Cl₅] exhibited from moderate to remarkable catalytic activities for ring-opening 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 OC₆Cl₅ analogue proceeded in a living manner even at 80 °C, 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)].
- Olefin metathesis,
- Molecular catalyst,
- Ring-opening metathesis polymerization,
- Cyclic olefin,
- Vanadium catalyst
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