Electronic structure of <i>N</i>‐sulfenylimines

Abstract

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CH 2 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 n N → 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CH 2 (R = H, Me, Cl, F, BH 2 ) systems. Copyright © 2003 John Wiley &amp; Sons, Ltd.