Metal-Free SF₆ Activation: A New SF₅ -Based Reagent Enables Deoxyfluorination and Pentafluorosulfanylation Reactions

The activation of SF₆ , a potent greenhouse gas, under metal-free and visible light conditions is reported. Herein, mechanistic investigations including EPR spectroscopy, NMR studies and cyclic voltammetry allowed the rational design of a new fluorinating reagent which was synthesized from the 2-electron activation of SF₆ with commercially available TDAE. This new SF₅ -based reagent was efficiently employed for the deoxyfluorination of CO₂ and the fluorinative desulfurization of CS₂ allowing the formation of useful fluorinated amines. Moreover, for the first time we demonstrated that our SF₅ -based reagent could afford the mild generation of Cl-SF₅ gas. This finding was exploited for the chloro-pentafluorosulfanylation of alkynes and alkenes.