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 Cα 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.
Insights into the electronic structure of
OsO2
using soft and hard x-ray photoelectron spectroscopy in combination with density functional theory