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.
Su, Jessica K., et al. "Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP." Angewandte Chemie (International Edition), vol. 58, no. 49, Oct. 2019. https://doi.org/10.1002/anie.201909688
Su, Jessica K., Jin, Zexin, Zhang, Rui, Lu, Gang, Liu, Peng, & Xia, Yan (2019). Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP. Angewandte Chemie (International Edition), 58(49). https://doi.org/10.1002/anie.201909688
Su, Jessica K., Jin, Zexin, Zhang, Rui, et al., "Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP," Angewandte Chemie (International Edition) 58, no. 49 (2019), https://doi.org/10.1002/anie.201909688
@article{osti_1571331,
author = {Su, Jessica K. and Jin, Zexin and Zhang, Rui and Lu, Gang and Liu, Peng and Xia, Yan},
title = {Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP},
annote = {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/anie.201909688},
url = {https://www.osti.gov/biblio/1571331},
journal = {Angewandte Chemie (International Edition)},
issn = {ISSN 1433-7851},
number = {49},
volume = {58},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2019},
month = {10}}