Metal-Free SF Activation: A New SF -Based Reagent Enables Deoxyfluorination and Pentafluorosulfanylation Reactions.

The activation of SF , 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 SF with commercially available TDAE. This new SF -based reagent was efficiently employed for the deoxyfluorination of CO and the fluorinative desulfurization of CS allowing the formation of useful fluorinated amines. Moreover, for the first time we demonstrated that our SF -based reagent could afford the mild generation of Cl-SF gas. This finding was exploited for the chloro-pentafluorosulfanylation of alkynes and alkenes.