Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Reactive intermediates

Radicals with multiple personalities

Nature Chemistry volume 5, pages 447–449 (2013)Cite this article

Subjects

A combined theoretical and experimental approach has revealed that radicals can be significantly stabilized by the presence of a remote anionic site in the same molecule. This finding has implications for understanding and potentially controlling the reactivity of these important reactive intermediates.

Such molecules can react in many ways, and predicting which path is taken requires precise knowledge of the energies of the orbitals holding the unpaired electron and the lone pair. Distonic structures can behave as 'ordinary' free radicals that undergo hydrogen-atom abstraction, recombination or disproportionation reactions. However, the energies of the relevant orbitals can be low enough that redox reactions are also possible. In addition, they can act as acids or bases — in either the Brønsted or the Lewis sense — through the ionic site.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Switching radical stability.

References

  1. Tomazela, D. M., Sabino, A. A., Sparrapan, R., Gozzo, F. C. & Eberlin, M. N. J. Am. Soc. Mass Spectrom. 17, 1014–1022 (2006).

    Article  CAS  Google Scholar 

  2. Stirk, K. M., Kiminkinen, L. K. M. & Kenttamaa, H. I. Chem. Rev. 92, 1649–1665 (1992).

    Article  CAS  Google Scholar 

  3. Tanko, J. M. & Phillips, J. P. J. Am. Chem. Soc. 121, 6078–80 (1999).

    Article  CAS  Google Scholar 

  4. Yang, J., Felton, G. A. N., Bauld, N. L. & Krische, M. J. J. Am. Chem. Soc. 126, 1634–1635 (2004).

    Article  CAS  Google Scholar 

  5. Giese, B. Acc. Chem. Res. 33 631–636 (2000).

    Article  CAS  Google Scholar 

  6. George, P., Siegbahn, P. E. M., Glusker, J. P. & Bock, C. W. J. Phys. Chem. B 103, 7531–7541 (1999).

    Article  CAS  Google Scholar 

  7. Sugawara, T., Komatsu, H. & Suzuki, K. Chem. Soc. Rev. 40, 3105–3118 (2011).

    Article  CAS  Google Scholar 

  8. Grin'ova, G., Marshall, D. L., Blanskby, S. J. & Coote, M. L. Nature Chem. 5, 474–481 10.1038/nchem.1625(2013).

    Article  CAS  Google Scholar 

  9. Verhoeven, J. W. & Pasman, P. Tetrahedron 37, 943–947 (1981).

    Article  CAS  Google Scholar 

  10. Hawker, C. J., Bosman, A. W. & Harth, E. Chem. Rev. 101, 3661–3688 (2001).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Malcolm Forbes is in the Department of Chemistry, Caudill Laboratories, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA,

    Malcolm D. E. Forbes

Authors
  1. Malcolm D. E. Forbes
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Malcolm D. E. Forbes.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Forbes, M. Radicals with multiple personalities. Nature Chem 5, 447–449 (2013). https://doi.org/10.1038/nchem.1663

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.1663

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing