Electronic structure of N-sulfenylimines

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 ppi-ppi bond and a relatively weak n(N) --> sigma*(S-R) anomeric pi 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 (C) 2003 John Wiley Sons, Ltd.