2010/07/26 by Martin Dračínský, Radek Pohl, Lenka Poštová Slavětínská +3
Chemistry · #Axial and Atropisomeric Chirality Synthesis #Free Radicals and Antioxidants #Molecular spectroscopy and chirality
paper · doi:10.1002/mrc.2658
openalex publication_date 2010/07/26 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/25
A series of model sulfides was oxidized in the NMR sample tube to sulfoxides and sulfones by the stepwise addition of meta-chloroperbenzoic acid in deuterochloroform. Various methods of quantum chemical calculations have been tested to reproduce the observed (1)H and (13)C chemical shifts of the starting sulfides and their oxidation products. It has been shown that the determination of the energy-minimized conformation is a very important condition for obtaining realistic data in the subsequent calculation of the NMR chemical shifts. The correlation between calculated and observed chemical shifts is very good for carbon atoms (even for the 'cheap' DFT B3LYP/6-31G* method) and somewhat less satisfactory for hydrogen atoms. The calculated chemical shifts induced by oxidation (the Delta delta values) agree even better with the experimental values and can also be used to determine the oxidation state of the sulfur atom (-S-, -SO-, -SO(2)-).