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

Abstract Reaction of [XeF][AsF 6 ] with excess KrF 2 at −78 °C in anhydrous HF (aHF) solvent has yielded the first mixed Kr II /Xe II noble‐gas compound, [FKrFXeF][AsF 6 ] ⋅0.5 KrF 2 ⋅2 HF, a salt of the [FKrFXeF] + cation. The potent oxidative fluorinating properties of Kr II fluoride species resulted in oxidation of Xe II to Xe IV in aHF at −60 °C to form the mixed Kr II /Xe IV cocrystals, ([Kr 2 F 3 ][AsF 6 ]) 2 ⋅XeF 4 and XeF 4 ⋅KrF 2 . Further decomposition at 22 °C resulted in oxidation of Xe IV to Xe VI to give the recently reported Kr II /Xe VI complexes, [F 5 Xe(FKrF) n ][AsF 6 ] ( n =1, 2), [F 5 Xe][AsF 6 ], and a new Kr II /Xe VI complex, [(F 5 Xe) 2 (μ‐FKrF)(AsF 6 ) 2 ], which was characterized by low‐temperature (LT) Raman spectroscopy. The [FKrFXeF][AsF 6 ]⋅0.5 KrF 2 ⋅2 HF, ([Kr 2 F 3 ][AsF 6 ]) 2 ⋅XeF 4 , and XeF 4 ⋅KrF 2 compounds were characterized by LT Raman spectroscopy and single‐crystal X‐ray diffraction. Quantum‐chemical calculations were used to assess the bonding in [FKrFXeF] + , [Kr 2 F 3 ] + , and [Xe 2 F 3 ] + and to aid in their vibrational assignments.