Synthesis and Characterization of [XeOXe]2+ in the Adduct‐Cation Salt, [CH3CN‐ ‐ ‐XeOXe‐ ‐ ‐NCCH3][AsF6]2

Abstract Acetonitrile and [FXeOXe‐ ‐ ‐FXeF][AsF 6 ] react at −60 °C in anhydrous HF (aHF) to form the CH 3 CN adduct of the previously unknown [XeOXe] 2+ cation. The low‐temperature X‐ray structure of [CH 3 CN‐ ‐ ‐XeOXe‐ ‐ ‐NCCH 3 ][AsF 6 ] 2 exhibits a well‐isolated adduct‐cation that has among the shortest Xe−N distances obtained for an sp‐hybridized nitrogen base adducted to xenon. The Raman spectrum was fully assigned by comparison with the calculated vibrational frequencies and with the aid of 18 O‐enrichment studies. Natural bond orbital (NBO), atoms in molecules (AIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses show that the Xe−O bonds are semi‐ionic whereas the Xe−N bonds may be described as strong electrostatic (σ‐hole) interactions.