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

COZZARÍN, MELINA V.; ROMANO, ROSANA M.

ChemistrySelect

Wiley Online Library

Lugar: Weinheim; Año: 2017 vol. 2 p. 4092 - 4098

Thephotochemistry of FC(O)SSCl isolated in solid Ar was investigated on the basisof the IR spectra of the matrices before and after different times ofbroad-band UV-visible irradiation. The first process occurring on broad-bandUV-visible irradiation was the transformation of the syn-gauche form of FC(O)SSClinto the anti-gauche conformer. FC(O)SCl and ClFC=O were produced, involvingthe loss of one or two sulfur atoms, respectively. Other mechanisms haveoriginated CO···ClSSF, OCS···ClSF, OCS···ClF, CO···ClSF and CS2···ClF molecularcomplexes, identified by the comparison of the experimental IR spectra withthat simulated with DFT (B3LYP/6-311+G*) calculations, with the exception of CS···ClF,which was assigned on the basis of the comparison with reported IR absorptions.