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.

  • Article
  • Published:

Isolation of a radical dianion of nitrogen oxide (NO)2−

Nature Chemistry volume 2, pages 644–647 (2010)Cite this article

Subjects

Abstract

Nitric oxide, NO, the diatomic hybrid of dinitrogen and dioxygen, has extensive biochemical, industrial and atmospheric chemistry. The unpaired electron on NO makes it highly reactive and its facile oxidation and reduction to make (NO)1+ and (NO)1−, respectively, have been heavily studied. Now the (NO)2− dianion has been isolated for the first time from the two-electron reduction of NO by the recently discovered (N2)3− yttrium complex {[(Me3Si)2N]2(THF)Y}2(µ3-η2:η2:η2-N2)K. NO reacts with this complex to form {[(Me3Si)2N]2(THF)Y}2(µ-η2:η2-NO), a paramagnetic complex that has an electron paramagnetic resonance spectrum definitive for the (NO)2− radical. Density functional theory reveals that a metal dπ to ligand π* interaction is crucial for the stability of this complex, which reacts with additional NO to generate the diamagnetic (ON=NO)2− product, {[(Me3Si)2N]2Y}4(µ3-ON=NO)2(THF)2.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Figure 1: Synthesis of complexes 1 and 2.
Figure 2: EPR spectra of the (NO)2− complexes and their simulated spectra.
Figure 3: Synthesis of complexes 3 and 4.
Figure 4: Thermal ellipsoid plot of {[(Me3Si)2N]2(THF)Y}2(μ-η2:η2-NO) (3).
Figure 5: Simplified molecular orbital scheme of {[(Me3Si)2N]2(THF)Y}2(µ-η2:η2-NO) (3).
Figure 6: Computed spin density of {[(Me3Si)2N]2(THF)Y}2(μ-η2:η2-NO) (3).

Similar content being viewed by others

References

  1. Koshland, Jr., D. E. The molecule of the year. Science 258, 1861 (1992).

    Article  PubMed  Google Scholar 

  2. Gray, H. B., Simon, J. D. & Trogler, W. C. Braving the Elements (University Science Books, 1995).

    Google Scholar 

  3. Schwartz, S. E. & White, W. H. Trace Atmospheric Constituents: Properties, Transformations, and Fates (John Wiley & Sons, 1983).

    Google Scholar 

  4. Ignarro, L. J. Nitric Oxide: Biology and Pathobiology (Academic Press, 2000).

    Google Scholar 

  5. Feelisch, M. & Stamler, J. S. Methods in Nitric Oxide Research (John Wiley and Sons, 1996).

    Google Scholar 

  6. Butler, A. R. & Williams, D. L. H. The physiological role of nitric oxide. Chem. Soc. Rev. 22, 233–241 (1993).

    Article  CAS  Google Scholar 

  7. Moncada, S., Palmer, R. M. J. & Higgs, E. A. Nitric oxide: physiology, pathophysiology, and pharmacology. Pharmacol. Rev. 43, 109–142 (1991).

    CAS  PubMed  Google Scholar 

  8. Palmer, R. M. J., Ferrige, A. G. & Moncada, S. Nitric oxide release accounts for the biological activity of endothelium-derived relaxing factor. Nature 327, 524–526 (1987).

    Article  CAS  PubMed  Google Scholar 

  9. Gusarov, I., Shatalin, K., Starodubtseva, M. & Nudler, E. Endogenous nitric oxide protects bacteria against a wide spectrum of antibiotics. Science 325, 1380–1384 (2009).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. McCleverty, J. A. Chemistry of nitric oxide relevant to biology. Chem. Rev. 104, 403–418 (2004).

    Article  CAS  PubMed  Google Scholar 

  11. Ford, P. C. & Lorkovic, I. M. Mechanistic aspects of the reactions of nitric oxide with transition-metal complexes. Chem. Rev. 102, 993–1018 (2002).

    Article  CAS  PubMed  Google Scholar 

  12. Farmer, P. J. & Sulc, F. Coordination chemistry of the HNO ligand with hemes and synthetic coordination complexes. J. Inorg. Biochem. 99, 166–184 (2005).

    Article  CAS  PubMed  Google Scholar 

  13. Montenegro, A. C. et al. Three redox states of nitrosyl: NO+, NO., and NO−/HNO interconvert reversibly on the same pentacyanoferrate(II) platform. Angew. Chem. Int. Ed. 48, 4213–4216 (2009).

    Article  CAS  Google Scholar 

  14. Stamler, J. S., Singel, D. J. & Loscalzo, J. Biochemistry of nitric oxide and its redox-activated forms. Science 258, 1898–1902 (1992).

    Article  CAS  PubMed  Google Scholar 

  15. Evans, W. J. et al. Isolation of dysprosium and yttrium complexes of a three-electron reduction product in the activation of dinitrogen, the (N2)3− radical. J. Am. Chem. Soc. 131, 11195–11202 (2009).

    Article  CAS  PubMed  Google Scholar 

  16. Kaim, W. & Sarkar, B. N2.3-: filling a gap in the N2n- series. Angew. Chem. Int. Ed. 48, 9409–9411 (2009).

    Article  CAS  Google Scholar 

  17. Evans, W. J. & Lee, D. S. Early developments in lanthanide-based dinitrogen reduction chemistry. Can. J. Chem. 83, 375–384 (2005).

    Article  CAS  Google Scholar 

  18. Evans, W. J., Lee, D. S., Lie, C. & Ziller, J. W. Expanding the LnZ3/alkali-metal reduction system to organometallic and heteroleptic precursors: formation of dinitrogen derivatives of lanthanum. Angew. Chem. Int. Ed. 43, 5517–5519 (2004).

    Article  CAS  Google Scholar 

  19. Evans, W. J. et al. Expanding dinitrogen reduction chemistry to trivalent lanthanides via the LnZ3/alkali metal reduction system: evaluation of the generality of forming Ln2(μ-η2:η2-N2) complexes via LnZ3/K. J. Am. Chem. Soc. 126, 14574–14582 (2004).

    Article  CAS  PubMed  Google Scholar 

  20. Evans, W. J., Lee, D. S., Ziller, J. W. & Kaltsoyannis, N. Trivalent [(C5Me5)2(THF)Ln]2(μ-η2:η2-N2) complexes as reducing agents including the reductive homologation of CO to a ketene carboxylate, (μ-η4-O2C-C=C=O)2-. J. Am. Chem. Soc. 128, 14176–14184 (2006).

    Article  CAS  PubMed  Google Scholar 

  21. Evans, W. J., Lorenz, S. E. & Ziller, J. W. Investigating metal size effects in the Ln2(μ-η2:η2-N2) reduction system: reductive reactivity with complexes of the largest and smallest trivalent lanthanide ions, La3+ and Lu3+. Inorg. Chem. 48, 2001–2009 (2009).

    Article  CAS  PubMed  Google Scholar 

  22. Krynitz, U., Gerson, F., Wiberg, N. & Veith, M. ESR spectra of radical anions of aliphatic azo compounds: tert-butyl and trimethylsilyl derivatives of diimine. Angew. Chem. Int. Ed. 8, 755–756 (1969).

    Article  CAS  Google Scholar 

  23. Bau, R., Sabherwal, I. H. & Burg, A. B. Preparation and structure of Co4(NO)8(NO2)2(N2O2). Novel complex containing a quadridentate hyponitrite group. J. Am. Chem. Soc. 93, 4926–4928 (1971).

    Article  CAS  Google Scholar 

  24. Arulsamy, N., Bohle, D. S., Imonigie, J. A. & Levine, S. An umpolung approach to cis-hyponitrite complexes. Angew. Chem. Int. Ed. 41, 2371–2373 (2002).

    Article  CAS  Google Scholar 

  25. Bottcher, H.-C., Graf, M., Mereiter, K. & Kirchner, K. Reductive dimerization of nitric oxide to trans-hyponitrite in the coordination sphere of a dinuclear ruthenium complex. Organometallics 23, 1269–1273 (2004).

    Article  Google Scholar 

  26. Villalba, M. E. C., Navaza, A., Güida, J. A., Varetti, E. L. & Aymonino, P. J. New structural study and reinterpretation of the vibrational spectra of the µ-N, O-hyponitrite bis[pentaamminecobalt(III)]4+ cation. Inorg. Chim. Acta 359, 707–712 (2006).

    Article  CAS  Google Scholar 

  27. Arulsamy, N., Bohle, D. S., Imonigie, J. A. & Moore, R. C. Group 8 and 10 hyponitrite and dinitrosyl complexes. Polyhedron 26, 4737–4745 (2007).

    Article  CAS  Google Scholar 

  28. Xu, N., Campbell, A. L. O., Powell, D. R., Khandogin, J. & Richter-Addo, G. B. A stable hyponitrite-bridged iron porphyrin complex. J. Am. Chem. Soc. 131, 2460–2461 (2009).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Černák, J. et al. Cyanocomplexes with one-dimensional structures: preparations, crystal structures and magnetic properties. Coord. Chem. Rev. 224, 51–66 (2002).

    Article  Google Scholar 

  30. Daff, P. J., Legzdins, P. & Rettig, S. J. The first nitrosyl complexes of niobium and tantalum. J. Am. Chem. Soc. 120, 2688–2689 (1998).

    Article  CAS  Google Scholar 

  31. Richter-Addo, G. B. & Legzdins, P. Metal Nitrosyls (Oxford University Press, 1992).

    Google Scholar 

  32. Huber, K. P. & Herzberg, G. Constants of diatomic molecules (data prepared by Gallagher, J. W. & Johnson, R. D. III) in NIST Chemistry WebBook, NIST Standard Reference Database Number 69 (eds Linstrom, P. J. & Mallard, W. G.) (National Institute of Standards and Technology, 2009).

    Google Scholar 

  33. Zuo, T. et al. M2@C79N (M=Y, Tb): isolation and characterization of stable endohedral metallofullerenes exhibiting M-M bonding interactions inside aza[80]fullerene cages. J. Am. Chem. Soc. 130, 12992–12997 (2008).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

Download references

Acknowledgements

We thank the US National Science Foundation for support of this research (CHE 0703372, 0723168, and 0809384), D. C. Lacy, E. Fadeev, M. J. Nilges and A. S. Borovik for help with EPR spectral studies, M. K. Takase for help with X-ray crystallography studies, and T. J. Mueller for assistance with the elemental analysis.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of California, Irvine, California, USA

    William J. Evans, Ming Fang, Jefferson E. Bates, Filipp Furche & Joseph W. Ziller

  2. Department of Chemistry and Biochemistry, University of California, Los Angeles, California, USA

    Matthew D. Kiesz & Jeffrey I. Zink

Authors
  1. William J. Evans
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ming Fang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jefferson E. Bates
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Filipp Furche
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Joseph W. Ziller
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Matthew D. Kiesz
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jeffrey I. Zink
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

W.J.E. and M.F. designed the study. Crystallography was done by J.W.Z. DFT calculations were done by J.E.B. and F.F. Raman spectra were obtained by M.D.K. and J.I.Z. All other experimental research was done by M.F. W.J.E. wrote the manuscript, which was reviewed and edited by all authors.

Corresponding author

Correspondence to William J. Evans.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 561 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Evans, W., Fang, M., Bates, J. et al. Isolation of a radical dianion of nitrogen oxide (NO)2−. Nature Chem 2, 644–647 (2010). https://doi.org/10.1038/nchem.701

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.701

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