Assessing Fluorosulfonyl Pentafluorooxosulfate (FSO ₂ –OSF ₅ ) Reservoir Capacity: Selective SOF ₄ , SO ₂ F ₂ , and [OSF ₅ ] ^– Anion Release

Abstract

Abstract Herein, the investigation of inorganic reagents containing the pentafluorooxosulfate (OSF 5 ) moiety is presented. First, the gram‐scale preparation of the reactive yet stable pentafluorosulfur hypofluorite (FOSF 5 ) as well as its spectroscopic data are reported. Then, the preparation and full characterization of the corresponding fluorosulfonyl pentafluorooxosulfate (FSO 3 SF 5 , FSPO ) by the fluoro‐pentafluorooxosulfanylation of SO 2 are highlighted. This liquid reagent (b.p. 39.6 °C) was later successfully used for modulable release of [cat][OSF 5 ] ion‐pair. The selective, in‐solution release of SOF 4 and SOF 4 /SO 2 F 2 species was also demonstrated. Finally, the SuFEx reactivity was investigated and showed interesting reservoir ability. Indeed, we report the one‐pot synthesis of sulfonyl fluoride (‐SO 2 F) and sulfurimidoyl fluoride (─N═S(O)F 2 ) species.