DFT and ab initio theoretical study for the CF3S + CO reaction

The potential energy surface for the reaction of CF3S with CO is calculated at the G4//B3LYP/6–311++G(d,p) level of theory. The results show that F-abstraction and addition–elimination mechanisms are involved, and the latter one is dominant thermodynamically and kinetically. The dominant channel is the reactant addition to form CF3SCO, and then decomposes to CF3 + OCS. While the direct F-abstraction channel and CF3SCO isomerization channel are not significant for the title reaction due to higher barriers involved. The comparisons among four reactions of CX3Y + CO (X = H, F; and Y = O, S) are made to imply the similar and different properties and reactivities of the same family elements and the F- and S-substituted derivatives.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideResearch highlights▶ The F-abstraction and addition–elimination mechanisms are involved in CF3S + CO reaction, and the latter one is dominant thermodynamically and kinetically. ▶ The dominant channel is the reactant addition to form CF3SCO, and then decomposes to CF3 + OCS. ▶ The comparisons among four reactions of CX3Y + CO (X = H, F; and Y = O, S) are made to imply the similar and different properties and reactivities of the same family elements and the F- and S-substituted derivatives.