Streamlining Thionyl Tetrafluoride (SOF4) and Pentafluorooxosulfate [OSF5]– Anions Syntheses

A one pot room temperature synthesis of thionyl tetrafluoride (SOF4) from elemental fluorine (F2) and thionyl fluoride (SOF2) is reported. The selective decagram scale process (100 mmol) allows a quantitative preparation of SOF4 with high purity. The solid‐state structure has also been elucidated and compared with the reported gas‐phase one. The use of this reagent for the formation of the emerging pentafluorooxosulfate [cat][OSF5] anions led to the preparation of multiple ion‐pairs (cat = Ag, NEt3Me, PPN, PPh4) in different organic solvents. The SuFEx reservoir ability of this anion was studied and by tuning the solvent system, the reactivity of pure thionyl tetrafluoride was observed using Ag[OSF5] in THF and acetone.