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

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. Nitric oxide, NO, has an unpaired electron and is widely used and studied in such diverse fields as biochemistry and atmospheric chemistry. Its radical nature means that singly charged species are common, but now two electrons have been added to give a radical dianion in an yttrium complex.

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

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