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Wang J, Kouznetsova TB, Niu Z, et al. Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry. Nat Chem. 2015;7(4):323-7doi: 10.1038/nchem.2185.
Wang, J., Kouznetsova, T. B., Niu, Z., Ong, M. T., Klukovich, H. M., Rheingold, A. L., Martinez, T. J., & Craig, S. L. (2015). Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry. Nature chemistry, 7(4), 323-7. https://doi.org/10.1038/nchem.2185
Wang, Junpeng, et al. "Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry." Nature chemistry vol. 7,4 (2015): 323-7. doi: https://doi.org/10.1038/nchem.2185
Wang J, Kouznetsova TB, Niu Z, Ong MT, Klukovich HM, Rheingold AL, Martinez TJ, Craig SL. Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry. Nat Chem. 2015 Apr;7(4):323-7. doi: 10.1038/nchem.2185. Epub 2015 Feb 23. PMID: 25803470.
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Nat Chem. 2015 Apr;7(4):323-7. doi: 10.1038/nchem.2185. Epub 2015 Feb 23.

Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry.

Nature chemistry

Junpeng Wang, Tatiana B Kouznetsova, Zhenbin Niu, Mitchell T Ong, Hope M Klukovich, Arnold L Rheingold, Todd J Martinez, Stephen L Craig

Affiliations

  1. Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
  2. Materials Science Division, Lawrence Livermore National Laboratory, Livermore, California 94550, USA.
  3. Department of Chemistry, University of California, La Jolla, California 92093, USA.
  4. Department of Chemistry, Stanford University, Stanford, California 94305, USA.

PMID: 25803470 DOI: 10.1038/nchem.2185

Abstract

Forbidden reactions, such as those that violate orbital symmetry effects as captured in the Woodward-Hoffmann rules, remain an ongoing challenge for experimental characterization, because when the competing allowed pathway is available the reactions are intrinsically difficult to trigger. Recent developments in covalent mechanochemistry have opened the door to activating otherwise inaccessible reactions. Here we report single-molecule force spectroscopy studies of three mechanically induced reactions along both their symmetry-allowed and symmetry-forbidden pathways, which enables us to quantify just how 'forbidden' each reaction is. To induce reactions on the ~0.1 s timescale of the experiments, the forbidden ring-opening reactions of benzocyclobutene, gem-difluorocyclopropane and gem-dichlorocyclopropane require approximately 130 pN less, 560 pN more and 1,000 pN more force, respectively, than their corresponding allowed analogues. The results provide the first experimental benchmarks for mechanically induced forbidden reactions, and in some cases suggest revisions to prior computational predictions.

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