A Bench-Stable Reagent for Divergent Synthesis and Storage of SF5X

Herein, we report a novel concept to promote the formation of mixed sulfur fluorides SF5Br and SF5Cl, pentafluoronitrosulfane SF5NO2, and disulfur decafluoride S2F10, divergently from a single, bench-stable, liquid, and commercially available organic reagent. Upon photoreaction with elemental bromine, liberation of SF5Br is observed in up to 87% yield. Consequently, after applying a chromoselectivity approach to purify the sulfur fluoride in the reaction mixture, SF5Br could be trapped by alkynes, affording access to SF5Br adducts in good to excellent yields of up to 81% over two steps. Furthermore, this concept could be extended to the release of SF5Cl by reaction with BrCl, affording SF5Cl in up to 82% yield. This reaction features an unprecedented halogenide-catalyzed halogen-methathesis reaction converting SF5Br into SF5Cl. At the same time, the reagent can act as a storage for SF5X with an improved safety profile and can release the molecule on demand. The storage of SF5X on industrial scale is a critical safety hazard that can be addressed by the reported method. Furthermore, the experimental findings are supported by in silico studies that reveal a critical stabilizing effect of the Si substituent.