Photoelectron spectra andab initio calculations of the electronic structure of amino-n-sulfenyl chlorides

The electronic structure of some amino-N-sulfenyl chlorides and related compounds is studied by photoelectron spectroscopy and ab initio calculations. Similar values of IP(n S ) and IP(n N ) and the total energy minimum indicate that in stable conformations the n S and n N orbitals are orthogonal. These conformers are characterized by an effective nN-σ S-Cl * interaction. The relationship between the intramolecular shift of charge and ionization potential values and the spatial structure of amino-N-sulfenyl chlorides is analyzed.