Structural and vibrational characterization of [KrF][AuF6] and α-[O2][AuF6] using single crystal X-ray diffraction, Raman spectroscopy and electron structure calculations

The salt [KrF][AuF6] has been prepared by the direct oxidation of gold powder in anhydrous HF at 20°C using the potent oxidative fluorinating agent KrF2. The KrF+ salt readily oxidizes molecular oxygen at ambient temperature to yield [O2][AuF6]. Variable temperature Raman spectroscopy has been used to identify a reversible phase transition in [O2][AuF6], which occurs between −114 and −118°C. Single crystal X-ray diffraction has been used to characterize the low-temperature, α-phase of [O2][AuF6]. The phase transition is attributed to ordering of the O2+ cation in the crystal lattice, which is accompanied by minor distortions of the AuF6− anion. The α-phase of [O2][AuF6] crystallizes in the triclinic space group P1̄, with a=4.935(6)Å, b=4.980(6)Å, c=5.013(6)Å, α=101.18(1)°, β=90.75(2)°, γ=101.98(2)°, V=342.97Å3, Z=1, and R1=0.0481 at −122°C. The structure of the precursor, [KrF][AuF6], has also been determined by single crystal X-ray diffraction and crystallizes in the monoclinic space group Cc with a=7.992(3)Å, b=7.084(3)Å, c=10.721(4)Å, β=105.58(1)°, V=584.8(4)Å3, Z=4 and R1=0.0389 at −125°C. The KrF+ and AuF6− ions interact by means of a FKr---FAu fluorine bridge that is bent by 125.3(7)° about the bridge fluorine. The KrFt and Kr---Fb bond lengths in [KrF][AuF6] were determined to be 1.76(1) and 2.15(1)Å, respectively. The energy minimized structures of the [KrF][AuF6] ion-pair and the AuF6− anion have been determined at the Hartree–Fock (HF), MP2 and local density functional (LDF) levels of theory. These calculations have also been used to assign the vibrational spectrum of the [KrF][AuF6] ion-pair in greater detail and to reassign the vibrational spectrum of the AuF6− anion.