Single-Molecule Observation of a Mechanically Activated Cis-to-Trans Cyclopropane Isomerization

The mechanochemical activation of cis-gem-difluorocyclopropane (cis-gDFC) mechanophore in toluene was characterized with single-molecule force spectroscopy. Unlike previously reported behavior in methyl benzoate (MB), two transitions are observed in the force vs extension curves of cis-gDFC polymers...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2016-08, Vol.138 (33), p.10410-10412
Main Authors: Wang, Junpeng, Kouznetsova, Tatiana B, Craig, Stephen L
Format: Article
Language:English
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Summary:The mechanochemical activation of cis-gem-difluorocyclopropane (cis-gDFC) mechanophore in toluene was characterized with single-molecule force spectroscopy. Unlike previously reported behavior in methyl benzoate (MB), two transitions are observed in the force vs extension curves of cis-gDFC polymers in toluene. The first transition occurs at the same force of ∼1300 pN observed previously in MB, but a second transition is observed at forces of ∼1800 pN that reveal the partial formation of the trans-gDFC isomer. The behavior is attributed to competing reactions of the cis-gDFC at the 1300 pN plateau: addition of oxygen to a ring-opened diradicaloid intermediate, and isomerization of cis-gDFC to its trans isomer.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b06452