Metal-Free SF 6 Activation: A New SF 5 -Based Reagent Enables Deoxyfluorination and Pentafluorosulfanylation Reactions.

The activation of SF 6 , 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 6 with commercially available TDAE. This new SF 5 -based reagent was efficiently employed for the deoxyfluorination of CO 2 and the fluorinative desulfurization of CS 2 allowing the formation of useful fluorinated amines. Moreover, for the first time we demonstrated that our SF 5 -based reagent could afford the mild generation of Cl-SF 5 gas. This finding was exploited for the chloro-pentafluorosulfanylation of alkynes and alkenes.