The Trifluoromethyl Sulfinyl and Oxathiyl Radicals

Zhuang Wu^+[a], Jian Xu^+[a] , Guohai Deng^[a], Xianxu Chu^[a], Liubov Sokolenko^[b], Tarek Trabelsi^[c], Joseph S. Francisco^*[d], Andr8 K. Eckhardt^[e], Peter R. Schreiner^*[e], and Xiaoqing Zeng^{* [a]}（曾小庆）

^[a] College of Chemistry, Chemical Engineering and Materials Science Soochow University Suzhou 215123 (P.R. China)

^[b] Organofluorine Chemistry Department, Institute of Organic Chemistry National Academy of Sciences of Ukraine Kiev-94 02660 (Ukraine)

^[c] University of Nebraska-Lincoln Lincoln, Nebraska 68526 (USA)

^[d] Department of Chemistry Purdue University West Lafayette, Indiana 47907 (USA)

^[e] Institute of Organic Chemistry Justus-Liebig University Heinrich-Buff-Ring 17, 35392 Giessen (Germany)

^{[ + ]} These authors contributed equally to this work.

Chem. Eur. J.2018, 24, 1505--508

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.

链接：http://onlinelibrary.wiley.com/doi/10.1002/chem.201705142/abstract