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New peroxynitrite–copper chemistry ensues via addition of nitric oxide (˙NO(g)) to a CuII–hydroperoxo species. In characterizing the system, the ligand–Cu(I) complex was shown to effect a seldom observed ˙NO(g) reductive coupling reaction. Biological implications are discussed.

Graphical abstract: Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(ii)–OOH species and a copper mediated NO reductive coupling reaction

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