Failed Attempts at Oxidation of XeF₆: Synthesis and Characterization of [Xe₂F₁₁][RuF₆]

Herein we report our attempts to oxidize XeF₆ using RuF₆ in anhydrous HF (aHF) under various conditions. Contrary to expectations of forming a Xe(VIII) species such as [XeF₇]⁺, the reactions consistently resulted in the formation of F₂ gas and, depending on the stoichiometric ratio, either the known compound [XeF₅][RuF₆] or the novel Xe(VI) compound [Xe₂F₁₁][RuF₆]. The latter was characterized by single-crystal X-ray diffraction and vibrational spectroscopy and studied with quantum chemical calculations. These, together with the consideration of reaction and lattice energies, suggest that an ionic solid containing [XeF₇]⁺ cations may be stable. However, we did not observe its formation under our reaction conditions, as the decomposition of [XeF₇]⁺ cations may be too fast in our case.