Mixed Noble-Gas Compounds of Krypton(II) and Xenon(VI); [F5 Xe(FKrF)AsF6 ] and [F5 Xe(FKrF)2 AsF6 ].

The coordination chemistry of KrF2 has been limited in contrast with that of XeF2 , which exhibits a far richer coordination chemistry with main-group and transition-metal cations. In the present work, reactions of [XeF5 ][AsF6 ] with KrF2 in anhydrous HF solvent afforded [F5 Xe(FKrF)AsF6 ] and [F5 Xe(FKrF)2 AsF6 ], the first mixed krypton/xenon compounds. X-ray crystal structures and Raman spectra show the KrF2 ligands and [AsF6 ]- anions are F-coordinated to the xenon atoms of the [XeF5 ]+ 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 XeF2 -KrF2 analogy and the limited chemistry of krypton by introducing a new class of coordination compound in which KrF2 functions as a ligand that coordinates to xenon(VI). The HF solvates, [F5 Xe(FH)AsF6 ] and [F5 Xe(FH)SbF6 ], are also characterized in this study and they provide rare examples of HF coordinated to xenon(VI).