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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.


ABSTRACT: 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.

SUBMITTER: Wijeratne GB 

PROVIDER: S-EPMC5630263 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

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

Wijeratne Gayan B GB   Hematian Shabnam S   Siegler Maxime A MA   Karlin Kenneth D KD  

Journal of the American Chemical Society 20170912 38


A copper complex, [Cu<sup>I</sup>(tmpa)(MeCN)]<sup>+</sup>, effectively reductively couples NO<sub>(g)</sub> 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 Cu<sup>I</sup> + NO<sub>(g)</sub>, leading to Cu<sup>I</sup>-mediated NO<sub>(g)</sub>-disproportionation. The relationship  ...[more]

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