Assessing Fluorosulfonyl Pentafluorooxosulfate (FSO2–OSF5) Reservoir Capacity: Selective SOF4, SO2F2, and [OSF5]– Anion Release

Herein, the investigation of inorganic reagents containing the pentafluorooxosulfate (OSF₅) moiety is presented. First, the gram-scale preparation of the reactive yet stable pentafluorosulfur hypofluorite (FOSF₅) as well as its spectroscopic data are reported. Then, the preparation and full characterization of the corresponding fluorosulfonyl pentafluorooxosulfate (FSO₃SF₅, FSPO) by the fluoro-pentafluorooxosulfanylation of SO₂ are highlighted. This liquid reagent (b.p. 39.6 °C) was later successfully used for modulable release of [cat][OSF₅] ion-pair. The selective, in-solution release of SOF₄ and SOF₄/SO₂F₂ 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 (-SO₂F) and sulfurimidoyl fluoride (─N═S(O)F₂) species.