Oxidation of ruthenium and iridium metal by XeF2 and crystal structure determination of [Xe2F3][RuF6]∙XeF2 and [Xe2F3][MF6] (M = Ru, Ir)

Abstract

Salts containing [Xe₂F₃]⁺ cations and [MF₆]^- anions (M = Ru, Ir) were synthesized by the oxidation of metal with excess of XeF₂ in anhydrous hydrogen fluoride (aHF) as a solvent. Single crystals of [Xe₂F₃][RuF₆]∙XeF₂, [Xe₂F₃][RuF₆] and [Xe₂F₃][IrF₆] were grown by slow evaporation of the solvent. [Xe₂F₃][RuF₆]∙XeF₂ crystallizes in a triclinic P-1 space group (a = 8.3362(1) Å, b = 8.8197(2) Å, c = 9.3026(4) Å; α = 68.27(1) °, β = 63.45(1) °, γ = 82.02 °, V = 568.09(9) ų (Z = 2)). Discrete [Xe₂F₃]⁺, XeF₂ and [RuF₆]^- units are found in the asymmetric unit. [Xe₂F₃][RuF₆] and [Xe₂F₃][IrF₆] compounds are isostructural and crystalize in a monoclinic C/c space group (a = 14.481(3) Å (Ru); 14.544(3) Å (Ir); b = 8.0837(8) Å (Ru), 8.0808(7) Å (Ir), c = 10.952(2) Å (Ru), 11.014(2) Å (Ir); β = 136.825(6) ° (Ru), 139.954(7) °,V = 877.2(3) ų (Ru), 883.6(3) ų (Ir); Z = 4). The asymmetric unit in the [Xe₂F₃][MF₆] (M = Ru, Ir) consists of one [Xe₂F₃]⁺  and one [MF₆]^- unit.