Synthesis and Characterization of [XeOXe](2+) in the Adduct-Cation Salt, [CH3 CN- - -XeOXe- - -NCCH3 ][AsF6 ]2

• Published in: Angewandte Chemie International Edition Vol. 55; no. 39; pp. 11917 - 11920
• Main Authors: DeBackere, John R, Bortolus, Mark R, Schrobilgen, Gary J
• Format: Journal Article
• Language: English
• Published: Germany 19.09.2016
• Subjects: xenon(II) oxides; fluorine chemistry; noble-gas chemistry; xenon-nitrogen bonds; σ-hole bonding
• DOI: 10.1002/anie.201606851

Acetonitrile and [FXeOXe- - -FXeF][AsF6 ] react at -60 °C in anhydrous HF (aHF) to form the CH3 CN adduct of the previously unknown [XeOXe](2+) cation. The low-temperature X-ray structure of [CH3 CN- - -XeOXe- - -NCCH3 ][AsF6 ]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.