Abstract: | The reaction of KPO2F2 with the strong Lewis acid SbF5 was studied as a potential pathway to the unknown PO2+ cation. The resulting product has the desired PO2SbF6 composition but consists of an eight‐membered, antimony‐oxygen‐phosphorus‐bridged ring that was characterized by vibrational and NMR spectroscopy, ab initio methods, and a single crystal x‐ray diffraction study. The preferred formation of the ring and its mechanism are discussed. |