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Copper(I)/NO(g) Reductive Coupling Producing a trans-Hyponitrite Bridged Dicopper(II) Complex: Redox Reversal Giving Copper(I)/NO(g) Disproportionation

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journal contribution
posted on 18.08.2017, 00:00 by Gayan B. Wijeratne, Shabnam Hematian, Maxime A. Siegler, Kenneth D. Karlin
A copper complex, [CuI(tmpa)­(MeCN)]+, effectively reductively couples NO(g) at RT in methanol (MeOH), giving a structurally characterized hyponitrito-dicopper­(II) adduct. Hydrogen-bonding from MeOH is critical for the hyponitrite complex formation and stabilization. This complex exhibits the reverse redox process in aprotic solvents, giving CuI + NO(g), leading to CuI-mediated NO(g)-disproportionation. The relationship of this chemistry to biological iron and/or copper mediated NO(g) reductive coupling to give N2O(g) is discussed.