Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP
Abstract
Abstract Ring‐opening metathesis polymerization (ROMP) has become one of the most important living polymerizations. Cyclopropenes (CPEs) remain underexplored for ROMP. Described here is that the simple swap of 1‐methyl to 1‐phenyl on 1‐(benzoyloxymethyl)CPEs elicited strikingly different modes of reactivity, switching from living polymerization to either selective single‐addition or living alternating ROMP. The distinct reactivity stems from differences in steric repulsions at the Ru alkylidene after CPE ring opening. Possible olefin or oxygen chelation from ring‐opened CPE substituents was also observed to significantly affect the rate of propagation. These results demonstrate the versatility of CPEs as a new class of monomers for ROMP, provide mechanistic insights for designing new monomers with rare single‐addition reactivity, and generate a new functionalizable alternating copolymer scaffold with controlled molecular weight and low dispersity.
- Authors:
-
[1];
[1];
[2];
[1]
- Department of Chemistry Stanford University Stanford CA 94305 USA
- Department of Chemistry University of Pittsburgh Pittsburgh PA 15260 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1571332
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 131 Journal Issue: 49; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Su, Jessica K., Jin, Zexin, Zhang, Rui, Lu, Gang, Liu, Peng, and Xia, Yan. Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP. Germany: N. p., 2019.
Web. doi:10.1002/ange.201909688.
Su, Jessica K., Jin, Zexin, Zhang, Rui, Lu, Gang, Liu, Peng, & Xia, Yan. Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP. Germany. https://doi.org/10.1002/ange.201909688
Su, Jessica K., Jin, Zexin, Zhang, Rui, Lu, Gang, Liu, Peng, and Xia, Yan. Tue .
"Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP". Germany. https://doi.org/10.1002/ange.201909688.
@article{osti_1571332,
title = {Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP},
author = {Su, Jessica K. and Jin, Zexin and Zhang, Rui and Lu, Gang and Liu, Peng and Xia, Yan},
abstractNote = {Abstract Ring‐opening metathesis polymerization (ROMP) has become one of the most important living polymerizations. Cyclopropenes (CPEs) remain underexplored for ROMP. Described here is that the simple swap of 1‐methyl to 1‐phenyl on 1‐(benzoyloxymethyl)CPEs elicited strikingly different modes of reactivity, switching from living polymerization to either selective single‐addition or living alternating ROMP. The distinct reactivity stems from differences in steric repulsions at the Ru alkylidene after CPE ring opening. Possible olefin or oxygen chelation from ring‐opened CPE substituents was also observed to significantly affect the rate of propagation. These results demonstrate the versatility of CPEs as a new class of monomers for ROMP, provide mechanistic insights for designing new monomers with rare single‐addition reactivity, and generate a new functionalizable alternating copolymer scaffold with controlled molecular weight and low dispersity.},
doi = {10.1002/ange.201909688},
journal = {Angewandte Chemie},
number = 49,
volume = 131,
place = {Germany},
year = {Tue Oct 22 00:00:00 EDT 2019},
month = {Tue Oct 22 00:00:00 EDT 2019}
}
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