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Electronic structure of S -nitrosothiols from sulfur K-edge X-ray absorption spectroscopy

TitleElectronic structure of S -nitrosothiols from sulfur K-edge X-ray absorption spectroscopy
Publication TypeJournal Article
Year of Publication2011
AuthorsMartin-Diaconescu, V, Perepichka, I, D Bohle, S, Kennepohl, P
JournalCan. J. Chem.
Volume89
Pagination93–97
Date Publishedfeb
ISSN0008-4042
KeywordsDFT, sulfur nitrosyls, XAS
Abstract

Sulfur K-edge X-ray absorption spectroscopy (S K-edge XAS) was applied to investigate the electronic structure of primary and tertiary S-nitrosothiols. Our experimental data, supported by density functional calculations, indicate that changes at C(alpha) affect the S-nitroso group through both inductive and direct orbital effects. Furthermore, our data are consistent with a weakening of the S-N bond in tertiary S-nitrosothiols as compared to their primary S-nitroso analogues. These results support existing computational models and suggest that the reactivity of S-nitrosothiols is not dominated by the electronics of the S-N bond.

URLhttp://www.nrcresearchpress.com/doi/abs/10.1139/V10-083
DOI10.1139/V10-083