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.

Automated summary

The activation of SF6 under metal-free and visible light conditions was investigated and a new fluorinating reagent was synthesized. This reagent was efficient in the deoxyfluorination of CO2 and fluorinative desulfurization of CS2 to produce useful fluorinated amines. Additionally, the reagent was able to generate Cl-SF5 gas, which was used for the chloro-pentafluorosulfanylation of alkynes and alkenes.