|Title||Electronic structure of S -nitrosothiols from sulfur K-edge X-ray absorption spectroscopy|
|Publication Type||Journal Article|
|Year of Publication||2011|
|Authors||Martin-Diaconescu, V, Perepichka, I, D Bohle, S, Kennepohl, P|
|Journal||Can. J. Chem.|
|Keywords||DFT, sulfur nitrosyls, XAS|
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.