NO Coupling at Copper to cis-Hyponitrite: N2O Formation via Protonation and H-Atom Transfer

Ghosh, Pokhraj; Stauffer, Molly; Hosseininasab, Valiallah; Kundu, Subrata; Bertke, Jeffery A.; Cundari, Thomas R.; Warren, Timothy H.

doi:10.1021/jacs.2c04033

Title: NO Coupling at Copper to cis-Hyponitrite: N₂O Formation via Protonation and H-Atom Transfer

Journal Article · 10 August 2022 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.2c04033 · OSTI ID:1909384

Ghosh, Pokhraj ^[1]; Stauffer, Molly ^[1]; Hosseininasab, Valiallah ^[2];

^[3];

^[2];

^[4];

^[1]

Michigan State Univ., East Lansing, MI (United States); Georgetown Univ., Washington, DC (United States)
Georgetown Univ., Washington, DC (United States)
Georgetown Univ., Washington, DC (United States); Indian Institute of Science Education and Research Thiruvananthapuram (India)
Univ. of North Texas, Denton, TX (United States)

Copper nitrite reductases (CuNIRs) convert NO₂^– to NO as well as NO to N₂O under high NO flux at a mononuclear type 2 Cu center. While model complexes illustrate N–N coupling from NO that results in symmetric trans-hyponitrite [Cu^II]– ONNO–[Cu^II] complexes, in this work we report NO assembly at a single Cu site in the presence of an external reductant Cp*₂M (M = Co, Fe) to give the first copper cis-hyponitrites [Cp*₂M]{[Cu^II](κ²- O₂N₂)[Cu^I]}. Importantly, the κ¹–N-bound [Cu^I] fragment may be easily removed by the addition of mild Lewis bases such as CNAr or pyridine to form the spectroscopically similar anion {[Cu^II](κ²-O₂N₂)}^–. The addition of electrophiles such as H⁺ to these anionic copper(II) cis-hyponitrites leads to N₂O generation with the formation of the dicopper(II)-bis-μ-hydroxide [Cu^II]₂(μ- OH)₂. One-electron oxidation of the {[Cu^II](κ²-O₂N₂)}^– core turns on H-atom transfer reactivity, enabling the oxidation of 9,10- dihydroanthracene to anthracene with concomitant formation of N₂O and [Cu^II]₂(μ-OH)₂. These studies illustrate both the reductive coupling of NO at a single copper center and a way to harness the strong oxidizing power of nitric oxide via the neutral cis- hyponitrite [Cu](κ²-O₂N₂).

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Research Organization:: Univ. of North Texas, Denton, TX (United States)

Sponsoring Organization:: National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15387

OSTI ID:: 1909384

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2156207: Experimental Crystal Structure Determination Pokhraj, Ghosh,; Molly, Stauffer,; Valiallah, Hosseininasab, https://doi.org/10.5517/ccdc.csd.cc2bcq2j The current record is supplemented by this dataset	dataset	January 2022
CCDC 2156208: Experimental Crystal Structure Determination Pokhraj, Ghosh,; Molly, Stauffer,; Valiallah, Hosseininasab, https://doi.org/10.5517/ccdc.csd.cc2bcq3k The current record is supplemented by this dataset	dataset	January 2022
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Title: NO Coupling at Copper to cis-Hyponitrite: N2O Formation via Protonation and H-Atom Transfer

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Title: NO Coupling at Copper to cis-Hyponitrite: N₂O Formation via Protonation and H-Atom Transfer