19457-88-6Relevant academic research and scientific papers
Xe3OF3+, a precursor to a noble-gas nitrate; Syntheses and structural characterizations of FXeONO2, XeF2·HNO3, and XeF2·N 2O4
Moran, Matthew D.,Brock, David S.,Mercier, Helene P. A.,Schrobilgen, Gary J.
, p. 13823 - 13839 (2010/11/05)
Xenon fluoride nitrate has been synthesized by reaction of NO2F with [FXeOXeFXeF][AsF6] at -50 °C. It was characterized in SO2ClF and CH3CN solutions by low-temperature 14N, 19F, and 129Xe NMR spectroscopy and in the solid state by low-temperature Raman spectroscopy (-160 °C) and single-crystal X-ray diffraction (-173 °C). The reactions were carried out using natural abundance and 18O-enriched [FXeOXeFXeF][AsF 6] and 15NO2F to aid in the vibrational assignments of FXeONO2 and to establish the likely reaction pathway. Raman spectroscopy showed that FXe16ON(16O18O) was formed, along with XeF2 and [NO2][AsF6], when an excess of N16O2F reacted with [FXe 18OXeFXeF][AsF6]. A reaction mechanism consistent with these findings is discussed. The crystal structure consists of well-separated FXeONO2 molecules which display no significant intermolecular interactions, providing geometric parameters that are in good agreement with the gas-phase values determined from quantum-chemical calculations. Decomposition of solid FXeONO2 is proposed to occur by three reaction pathways to give XeF2, Xe, O2, N2O5, N 2O4, and NO2F. Attempts to synthesize FXeONO2 and Xe(ONO2)2 by reaction of XeF 2 with HNO3 in SO2ClF solution below -30 °C led to XeF2·HNO3. The structure of XeF 2?HNO3 includes a hydrogen bond between HNO 3 and a fluorine atom of XeF2, as well as an interaction between the xenon atom and an oxygen atom of HNO3, leading to a crystal lattice comprised of layered sheets. A molecular addition compound between XeF2 and N2O4 crystallized from liquid N2O4 below 0 °C. The crystal structure of XeF 2?N2O4 displayed weak interactions between the xenon atom of XeF2 and the oxygen atoms of N2O 4. Quantum-chemical calculations have been used to assign the vibrational spectra of FXeONO2, XeF2·HNO 3, and XeF2?N2O4 and to better understand the nature of the interactions of HNO3 and N 2O4 with XeF2. The synthesis of [XeONO 2][AsF6] was attempted by the reaction of FXeONO 2 with excess liquid AsF5 between -78 and -50 °C, but resulted in slow formation of [NO2][AsF6], Xe, and O 2. Thermodynamic calculations show that the pathways to [XeONO 2][AsF6] formation and decomposition are exothermic and spontaneous under standard conditions and at -78 °C.
