Unimolecular Photochemical Mechanisms of FC(O)SSCl Isolated in Solid Ar

Abstract

The photochemistry of FC(O)SSCl isolated in solid Ar was investigated on the basis of the IR spectra of the matrices before and after different times of broad‐band UV‐visible irradiation. The first process occurring on broad‐band UV‐visible irradiation was the transformation of the syn‐gauche form of FC(O)SSCl into the anti‐gauche conformer. FC(O)SCl and ClFC=O were produced, involving the loss of one or two sulfur atoms, respectively. Other mechanisms have originated CO⋅⋅⋅ClSSF, OCS⋅⋅⋅ClSF, OCS⋅⋅⋅ClF, CO⋅⋅⋅ClSF and CS2⋅⋅⋅ClF molecular complexes, identified by the comparison of the experimental IR spectra with that simulated with DFT (B3LYP/6‐311+G*) calculations, with the exception of OCS⋅⋅⋅ClF