The osmium(VIII) oxofluoro cations osmium dioxide trifluoride (1) and bis[cis osmium dioxide tetrafluoride]fluorine (2): synthesis, characterization by F-19 NMR spectroscopy and Raman spectroscopy, and X-ray crystal structure of an antimony fluoride dimer complex with (2) and density functional theory calculations of (1), (2) and rhenium dioxide trifluoride.

Osmium dioxide tetrafluoride, cw-OsO2F4, reacts with the strong fluoride ion acceptors AsF5 and SbF5 in anhydrous HF and SbF5 solutions to form orange salts. Raman spectra are consistent with the formation of the fluorine-bridged diosmium cation F(cis-OsO2F3)2⁺, as the AsF6^- and Sb2F11^- salts, respectively. The ¹⁹F NMR spectra of the salts in HF solution are exchange-averaged singlets occurring at higher frequency than those of the fluorine …