Mixed Noble‐Gas Compounds of Krypton(II) and Xenon(VI); [F<sub>5</sub>Xe(FKrF)AsF<sub>6</sub>] and [F<sub>5</sub>Xe(FKrF)<sub>2</sub>AsF<sub>6</sub>]
Matic Lozinšek, Hélène P. A. Mercier, Gary J. Schrobilgen
Abstract
Abstract 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).