Vibrational and Valence Photoelectron Spectroscopies, Matrix Photochemistry, and Conformational Studies of ClC(O)SSCl
2011-09-15T00:00:00Z (GMT) by
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 the gas phase present four distinct regions, corresponding to ionizations from electrons formally located at the S, O, and Cl atoms and at the CO bond. The vibrational IR and Raman spectra of the liquid were interpreted in terms of the most stable syn–gauche conformer (the OC double bond syn with respect to the SS single bond and the CS single bond gauche with respect to the SCl single bond) in equilibrium with the less stable anti–gauche form, both occurring in two enantiomeric 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.
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