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Updated: Jan 6, 2026

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Tuning the Reactivity of Cyclopropenes from Living Ring-Opening Metathesis Polymerization (ROMP) to Single-Addition
Jessica K Su1, Zexin Jin1, Rui Zhang2
1Department of Chemistry, Stanford University, Stanford, CA, 94305, USA.
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.
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