Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H
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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
August 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 H 2 S and Nitroso Chemistries.” Journal of the American Chemical Society, vol. 138, no. 36, Sept. 2016, pp. 11441–44. © 2016 American Chemical Society
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Author's final manuscript
Abstract
Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H[superscript 2]S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H[subscript 2]S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H[superscript 2]S + N[subscript 2]O[subscript 3] → HSNO + HNO[subscript 2], where N[superscript 2]O[superscript 3] is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H[subscript 2]S 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
