Transforming the most powerful greenhouse gas into compounds of interest

Publication of the LCH in the journal Angewandte Chemie International Edition on April 24, 2022. CNRS-INSB communication on May 24, 2022. 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.