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Hou X, Nomura K. Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization. J Am Chem Soc. 2016;138(36):11840-9doi: 10.1021/jacs.6b06330.
Hou, X., & Nomura, K. (2016). Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization. Journal of the American Chemical Society, 138(36), 11840-9. https://doi.org/10.1021/jacs.6b06330
Hou, Xiaohua, and Nomura, Kotohiro. "Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization." Journal of the American Chemical Society vol. 138,36 (2016): 11840-9. doi: https://doi.org/10.1021/jacs.6b06330
Hou X, Nomura K. Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization. J Am Chem Soc. 2016 Sep 14;138(36):11840-9. doi: 10.1021/jacs.6b06330. Epub 2016 Aug 29. PMID: 27539652.
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J Am Chem Soc. 2016 Sep 14;138(36):11840-9. doi: 10.1021/jacs.6b06330. Epub 2016 Aug 29.

Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization.

Journal of the American Chemical Society

Xiaohua Hou, Kotohiro Nomura

Affiliations

  1. Department of Chemistry, Faculty of Science and Engineering, Tokyo Metropolitan University , 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, Japan.

PMID: 27539652 DOI: 10.1021/jacs.6b06330

Abstract

Ring-opening metathesis polymerization (ROMP) of various cyclic olefins especially using three (arylimido)vanadium(V)-alkylidene catalysts, V(CHSiMe3)(N-2,6-Cl2C6H3) (OC6F5) (PMe3)2 (3), V(CHSiMe3) (NR)[OC(CF3)3](PMe3)2 [R = Ph (6), 2,6-Cl2C6H3 (7)] have been explored. Complex 3 exhibited the highest catalytic activity (ex. TOF = 603 000 h(-1), 168 s(-1)) for ROMP of norbornene (NBE) among a series of (imido)vanadium(V)-alkylidenes, and the cis-specific living ROMPs of NBE proceeded with remarkable activities (TOF = 125 000-157 000 h(-1) at 25 °C) by the fluorinated alkoxo analogues (6, 7). The activities by 6, 7 increased at high temperature (50 and 80 °C) and/or upon addition of PMe3 without decrease in the cis selectivity (98%). The ROMPs in the presence of 1-hexene by 3, 7 proceeded without significant decrease in the activities, and the Mn values could be controlled by degree of chain transfer (cross metathesis). These dichlorophenylimido analogues (3, 7) were effective for ROMPs of various norbornene derivatives; ROMP of cyclooctene took place by 3, and the activity increased at high temperature (50, 80 °C).

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