Tuning the Reactivity of Cyclopropenes from Living Ring-Opening Metathesis Polymerization (ROMP) to Single-Addition and Alternating ROMP
Jessica K. Su
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorZexin Jin
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorRui Zhang
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260 USA
Search for more papers by this authorGang Lu
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Peng Liu
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Yan Xia
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorJessica K. Su
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorZexin Jin
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorRui Zhang
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260 USA
Search for more papers by this authorGang Lu
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Peng Liu
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Yan Xia
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorGraphical Abstract
A simple change in the substituents on cyclopropene rings elicited strikingly different modes of metathesis reactivity, switching from living homopolymerization to either selective single-addition or alternating copolymerization. In both cases well-controlled polymers were obtained.
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.
Conflict of interest
The authors declare no conflict of interest.
Supporting Information
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