Vibrational and Valence Photoelectron Spectroscopies, Matrix Photochemistry, and Conformational Studies of ClC(O)SSCl

Abstract

ClC(O)SSCl was prepared by an improved method by the reaction of [(CH3)2CHOC(S)]2S with SO2Cl2 in hexane. The photoelectron spectra in gas phase present four distinct regions, corresponding to ionizations from electrons formally located at the S, O and Cl atoms and at the C=O bond. The vibrational IR and Raman spectra of the liquid were interpreted in terms of the most stable syn-gauche conformer (the O=C double bond syn with respect to the S-S single bond and the C-S single bond gauche with respect to the S-Cl single bond) in equilibrium with the less stable anti-gauche form, both occurring in two enanthiomeric forms. The randomization process between the conformers was induced by broad-band UV-visible irradiation in matrix conditions, and several photoproducts were identified by FTIR spectroscopy. The experimental results were complemented by theoretical calculations.