title: Synthesis and Characterization of [XeOXe](2+) in the Adduct-Cation Salt, [CH3 CN- - -XeOXe- - -NCCH3 ][AsF6 ]2.
abstract: 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.
authors: Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1, Canada.
authors: John R
authors: JR
authors: De Backere
authors: Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1, Canada.
authors: Mark R
authors: MR
authors: Bortolus
authors: Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1, Canada. schrobil@mcmaster.ca.
authors: Gary J
authors: 0000-0001-5109-6979
authors: GJ
authors: Schrobilgen
keywords: fluorine chemistry; noble-gas chemistry; xenon(II) oxides; xenon-nitrogen bonds; σ-hole bonding