Mixed Noble‐Gas Compounds of Krypton(II) and Xenon(VI); [F(5)Xe(FKrF)AsF(6)] and [F(5)Xe(FKrF)(2)AsF(6)]

The coordination chemistry of KrF(2) has been limited in contrast with that of XeF(2), which exhibits a far richer coordination chemistry with main‐group and transition‐metal cations. In the present work, reactions of [XeF(5)][AsF(6)] with KrF(2) in anhydrous HF solvent afforded [F(5)Xe(FKrF)AsF(6)] and [F(5)Xe(FKrF)(2)AsF(6)], the first mixed krypton/xenon compounds. X‐ray crystal structures and Raman spectra show the KrF(2) ligands and [AsF(6)](−) anions are F‐coordinated to the xenon atoms of the [XeF(5)](+) cations. Quantum‐chemical calculations are consistent with essentially noncovalent ligand−xenon bonds that may be described in terms of σ‐hole bonding. These complexes significantly extend the XeF(2)–KrF(2) analogy and the limited chemistry of krypton by introducing a new class of coordination compound in which KrF(2) functions as a ligand that coordinates to xenon(VI). The HF solvates, [F(5)Xe(FH)AsF(6)] and [F(5)Xe(FH)SbF(6)], are also characterized in this study and they provide rare examples of HF coordinated to xenon(VI).