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

Kotohiro Nomura; Sapanna Chaimongkolkunasin

doi:10.1007/s10118-019-2298-9

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

FEATURE ARTICLE | Updated：2021-02-18

- (Arylimido)vanadium(V)-Alkylidene Complexes as Catalysts for Ring-opening Metathesis Polymerization (ROMP) of Cyclic Olefins: Ligand Design for Exhibiting the High Activity
- (Arylimido)vanadium(V)-Alkylidene Complexes as Catalysts for Ring-opening Metathesis Polymerization (ROMP) of Cyclic Olefins: Ligand Design for Exhibiting the High Activity
- Chinese Journal of Polymer Science 2019年37卷第10期页码：943-950
- Affiliations：
  
  Department of Chemistry Graduate School of Science, Tokyo Metropolitan University, Japan
- Author bio：
  
  ktnomura@tmu.ac.jp
- Funds：
  
  K. N. expresses his heartfelt thanks to former/present group members who contributed this project as coauthors, and the other members for discussion/supports. This project was 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, and Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (JSPS, Nos. 15H03812, 18H01982). S. C. acknowledges the Tokyo Metropolitan government (Tokyo Human Resources Fund for City Diplomacy) for pre-doctoral fellowship.
- DOI：10.1007/s10118-019-2298-9
  中图分类号：
- 收稿：2019-05-05，
  
  修回：2019-5-17，
  
  录用：2019-5-17，
  
  网络首发：2019-06-28，
  
  纸质出版：2019-10
- Accepted：
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Nomura, K.; Chaimongkolkunasin, S. (Arylimido)vanadium(V)-alkylidene complexes as catalysts for ring-opening metathesis polymerization (ROMP) of cyclic olefins: Ligand design for exhibiting the high activity. Chinese J. Polym. Sci. 2019, 37, 943–950.

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.
Nomura, K.; Chaimongkolkunasin, S. (Arylimido)vanadium(V)-alkylidene complexes as catalysts for ring-opening metathesis polymerization (ROMP) of cyclic olefins: Ligand design for exhibiting the high activity. Chinese J. Polym. Sci. 2019, 37, 943–950. DOI： 10.1007/s10118-019-2298-9.

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.

摘要

Abstract

(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe

)(NR)(ORʹ)(PMe

)

[R = Ad

6-Me

6-Cl

; Rʹ = 2

6-Me

6-F

] 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(CHSiMe

)(N-2

6-Cl

)(OC

)(PMe

)

(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 OC

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(CHSiMe

)(NC

)(O-2

)(PMe

)

with 1.0 equiv. of C

OH or C

via

immediate phenoxy exchange; the activity was affected by the kind of phenol added [TOF in the ROMPs of NBE: 4.62 × 10

min

–1

(upon addition of C

OH) versus 37.3 min

–1

(none)].

关键词

Keywords

references

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