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

Nature Chemistry volume 2, pages 644647 (2010) | Download Citation

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}23222-N2)K. NO reacts with this complex to form {[(Me3Si)2N]2(THF)Y}2(µ-η22-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}43-ON=NO)2(THF)2.

  • Compound C32H88N6O2Si8Y2

    {[(Me3Si)2N]2(THF)Y}2(μ-η2:η2-N2)

  • Compound C32H88KN6O2Si8Y2

    {[(Me3Si)2N]2(THF)Y}2(μ3-η2:η2:η2-N2)K

  • Compound C32H88N5O3Si8Y2

    {[(Me3Si)2N]2(THF)Y}2(μ-η2:η2-NO)

  • Compound C56H160N12O6Si16Y4

    {[(Me3Si)2N]2Y}4(μ3-ON=NO)2(THF)2

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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.

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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

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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.

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The authors declare no competing financial interests.

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Correspondence to William J. Evans.

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DOI

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