A new reagent has been designed through 2-electron activation of SF₆ with commercially available tetrakis(dimethylamino)ethylene (TDAE) under blue LED irradiation. The versatility of this new SF₅-based reagent has been demonstrated for the deoxyfluorination of CO₂ and the fluorinative desulfurization of CS₂ affording useful fluorinated amines. Moreover, SF₅Cl could be generated under mild conditions from reagent I allowing chloro-pentafluorosulfanylation of alkenes and alkynes.

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.

Credits: Anis Tlili

Reference: Metal-Free SF6 Activation: A New SF5-Based Reagent Enables Deoxyfluorination and Pentafluorosulfanylation Reactions. Alexis Taponard, Tristan Jarrosson, Maurice Médebielle, Lhoussain Khrouz, Julie Broggi and Anis Tlili. Angewandte Chemie International Edition, April 24,2022.
DOI : https://doi.org/10.1002/anie.202204623