On the XeF+/H2O System: Synthesis and Characterization of the Xenon (II) Oxide Fluoride Cation, FXeOXeFXeF+ (PREPRINT)
Abstract
The reported synthesis of the H2OF+ cation as a product of the oxidative fluorination of H2O by [XeF][PnF6] (Pn = As, Sb) in HF solution has been reinvestigated. The system exhibits complex equilibria, producing two new Xe(II) compounds, [Xe3OF3][PnF6] and [H3O][PnF6]2XeF2, refuting the original claim for the synthesis of the H2OF+ cation. Both compounds have been isolated and characterized by vibrational spectroscopy and single-crystal X-ray diffraction. The X-ray crystal structures of the [Xe3OF3][PnF6] salts contain the Z-shaped FXeOXeFXeF+ cation, which represents the first example of an isolated Xe(II) oxide fluoride. The crystal structure of the [H3O][AsF6]2XeF2 adduct contains XeF2 molecules that interact with the H3O+ cations. The vibrational assignments for the Xe3OF3+ cation have been made with the aid of quantum-chemical calculations and were confirmed by (sup 18)O-enrichment, while the assignments for [H3O][AsF6]2XeF2 were confirmed by 2D- and (sup 18)O-enrichment. Quantum-chemical calculations have also been carried out for H3O+nXeF2 (n = 14), and have been used to interpret the X-ray crystal structure and vibrational spectra of [H3O][AsF6]2XeF2. The energy-minimized geometries and vibrational frequencies for HOF and H2OF+ have been calculated, further disproving the original report of the H2OF+ cation. Both FXeOH and FXeOH2+ have also been computed and are viable intermediates in the proposed equilibria between XeF+ and H2O that lead to the Xe3OF3+ cation.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jun 30, 2009
- Accession Number
- ADA513621
Entities
People
- Bernard E. Pointner
- Berthold Hoge
- Gary J. Schrobilgen
- Helene P. Mercier
- Jerry A. Boatz
- Karl O. Christe
- Matthew D. Moran
- Michael Gerken
Organizations
- Air Force Research Laboratory