@article {ISI:000287150300002, title = {Electronic structure of S -nitrosothiols from sulfur K-edge X-ray absorption spectroscopy}, journal = {Can. J. Chem.}, volume = {89}, number = {2}, year = {2011}, month = {feb}, pages = {93{\textendash}97}, 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.}, keywords = {DFT, sulfur nitrosyls, XAS}, issn = {0008-4042}, doi = {10.1139/V10-083}, url = {http://www.nrcresearchpress.com/doi/abs/10.1139/V10-083}, author = {Martin-Diaconescu, Vlad and Perepichka, Inna and Bohle, D Scott and Kennepohl, Pierre} }