Electronic structure ofN-sulfenylimines

Abstract

The electronic structure of N‐sulfenylimines was studied in detail using ab initio MO and density functional methods. The S—N rotational barriers and N‐inversion barriers in HS—NCH2 at the G2MP2 level were found to be 5.60 and 21.76 kcal mol−1, respectively. There is a partial pπ–pπ bond and a relatively weak nN → σ*S—R anomeric π bond between sulfur and nitrogen in N‐sulfenylimines. NBO analysis was carried out to estimate quantitatively the above delocalizations in RS—NCH2 (R = H, Me, Cl, F, BH2) systems.