Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries
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Spontaneous and selective formation of HSNO.pdf
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Author(s)
Martin-Drumel, Marie-Aline
Lopez, Christopher A.
Crabtree, Kyle N.
Nguyen, Thanh L.
Thorwirth, Sven
Stanton, John F.
McCarthy, Michael C.
Nava, Matthew Jordan
Womack, Caroline C.
Cummins, Christopher C
Date Issued
September 2016
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Nava, Matthew, et al. “Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries.” Journal of the American Chemical Society 138, 36 (August 2016): 11441–11444 © 2016 American Chemical Society
Version
Author's final manuscript
Abstract
Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H₂S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H₂S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H₂S + N₂O₃ → HSNO + HNO₂, where N₂O₃ is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H₂S may form HNO and HSSH. The length of the S-N bond has been derived to high precision and is found to be unusually long: 1.84 Å, the longest S-N bond reported to date for an R-SNO compound. The present structural and, particularly, reactivity investigations of this elusive molecule provide a firm foundation to better understand its potential physiological chemistry and propensity to undergo S-N bond cleavage in vivo.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/JACS.6B05886
