Radical disproportionation Puns

A radical N2O2.− intermediate formed during a nitric oxide reductive coupling reaction was captured at a copper center in a metal–organic framework (MOF). Strict site isolation in the solid state is key in stabilizing this intermediate.

Abstract

Dianionic hyponitrite (N2O22−) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme‐copper oxidases and nitric oxide reductases. In this work, we examine the gas‐solid reaction of nitric oxide with the metal–organic framework CuI‐ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N2O2.− intermediate. These results highlight the advantage provided by site‐isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one‐electron couple in these enzymes.

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Journal of the American Chemical SocietyDOI: 10.1021/jacs.9b13503

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I actually agree with him! 😲

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>He doesn’t care how great a person may be, and he pays no more attention to the rich than to the poor. He made them all. Job 34:19 NLT