Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKrIIFXeIIF][AsF6]⋅0.5 KrIIF2⋅2 HF, ([KrII2F3][AsF6])2⋅XeIVF4, and XeIVF4⋅KrIIF2

Abstract

AbstractReaction of [XeF][AsF6] with excess KrF2 at −78 °C in anhydrous HF (aHF) solvent has yielded the first mixed KrII/XeII noble‐gas compound, [FKrFXeF][AsF6] ⋅0.5 KrF2⋅2 HF, a salt of the [FKrFXeF]+ cation. The potent oxidative fluorinating properties of KrII fluoride species resulted in oxidation of XeII to XeIV in aHF at −60 °C to form the mixed KrII/XeIV cocrystals, ([Kr2F3][AsF6])2⋅XeF4 and XeF4⋅KrF2. Further decomposition at 22 °C resulted in oxidation of XeIV to XeVI to give the recently reported KrII/XeVI complexes, [F5Xe(FKrF)n][AsF6] (n=1, 2), [F5Xe][AsF6], and a new KrII/XeVI complex, [(F5Xe)2(μ‐FKrF)(AsF6)2], which was characterized by low‐temperature (LT) Raman spectroscopy. The [FKrFXeF][AsF6]⋅0.5 KrF2⋅2 HF, ([Kr2F3][AsF6])2⋅XeF4 , and XeF4⋅KrF2 compounds were characterized by LT Raman spectroscopy and single‐crystal X‐ray diffraction. Quantum‐chemical calculations were used to assess the bonding in [FKrFXeF]+, [Kr2F3]+, and [Xe2F3]+ and to aid in their vibrational assignments.