Electronic structure of N‐sulfenylimines

Abstract

AbstractThe 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. Copyright © 2003 John Wiley & Sons, Ltd.