Journal article

Publication year: 2018

Pages: 1505-1508

Journal: Chemistry - A European Journal

Volume number: 24

Issue number: 7

DOI Link: https://doi.org/10.1002/chem.201705142

Publisher: Wiley

Abstract: 

Two hitherto unreported sulfur‐centered radicals CF₃SO^. and CF₃OS^. were generated in the gas phase through high‐vacuum flash pyrolyses of sulfoxide CF₃S(O)X (X=CF₃, Cl, PhO) precursors. The CF₃OS^.
molecule is the first experimental example that constitutes an oxathiyl
radical. It was isolated and characterized by combining
matrix‐isolation IR and UV/Vis spectroscopy with quantum chemical
computations up to the UCCSD(T)‐F12/cc‐pVTZ‐F12 level of theory. Upon UV
light irradiation (254 or 266 nm), sulfinyl radical (CF₃SO^.) isomerizes to oxathiyl radical (CF₃OS^.)
in cryogenic noble gas matrices (Ar and Ne). Natural population
analyses at the BP86/def2‐TZVPP//UCCSD(T)‐F12/cc‐pVTZ‐F12 level suggest
that the spin density in CF₃OS^. is mainly localized on the sulfur atom (0.86), whereas, in CF₃SO^. the spin density is almost equally distributed on the sulfur (0.55) and oxygen (0.43) atoms.

Harvard Citation style: Wu, Z., Xu, J., Deng, G., Chu, X., Sokolenko, L., Trabelsi, T., et al. (2018) The Trifluoromethyl Sulfinyl and Oxathiyl Radicals, Chemistry - A European Journal, 24(7), pp. 1505-1508. https://doi.org/10.1002/chem.201705142

APA Citation style: Wu, Z., Xu, J., Deng, G., Chu, X., Sokolenko, L., Trabelsi, T., Franciso, J., Eckhardt, A., & Schreiner, P. (2018). The Trifluoromethyl Sulfinyl and Oxathiyl Radicals. Chemistry - A European Journal. 24(7), 1505-1508. https://doi.org/10.1002/chem.201705142