| This Thesis extends the fundamental chemistry of the noble-gas elements, namely, xenon and krypton. More specifically, the chemistry of Xe(IV) has been extended by the synthesis and characterization of Xe(IV) oxide and oxide fluoride derivatives. The syntheses of XeOF2, F2OXeN≡CCH 3, and XeOF2 ˙nHF and their structural characterizations are described. All three compounds are endothermic and explosive at temperatures approaching 0 °C. Although XeOF2 had been previously reported, it had not been isolated as a pure compound. Xenon oxide difluoride has now been characterized in CH3CN solution by 19F, 17O, and 129Xe NMR spectroscopy and XeOF2, F2OXeN≡CCH3, and XeOF2 ˙ nHF have been characterized in the solid-state by Raman spectroscopy.;The [H(OXeF2)n][AsF6] and [FXeII(OXeIVF2)n][AsF6] (n = 1, 2) salts have been synthesized and structurally characterized in the solid state by low-temperature Raman spectroscopy. The chain length of each cation is limited to one or two OXeF2 subunits, which are oxygen-bridged and are strongly ion-paired with the AsF6 - anion. The reaction of XeOF2 ˙xHF in superacidic HF/SbF5 solvent mixtures resulted in a mixture of ([XeF3 ˙HF][Sb2F11])2·[H 5F4][SbF6], [XeF3 ˙HF][Sb 2F11], and [XeF3][SbF6].;The syntheses and structural characterizations of [XOF2][AsF 6] (X = Cl, Br), the XeF2 adduct-salts, [BrOF2][AsF 6]·nXeF2 (n = 1, 2), and the KrF2 adduct-salt, [BrOF2][AsF6]˙2KrF 2, are also described. The crystal structure of [BrOF2][AsF 6] shows a positional disorder among the oxygen atom and the fluorine atoms. The low-temperature Raman spectra of [XOF2][AsF6], the complex cation salts, [BrOF2][AsF6]· nXeF2 (n = 1,2), and [BrOF2][AsF 6]·2KrF2 have been assigned on the basis of the crystal structures and with the aid of quantum-chemical calculations.;The syntheses of FXeON16O2 and FXeONe( 18OO) has shed light on the mechanism leading to the formation of FXeONO2. Raman spectroscopy indicated the absence of 16/18 O isotopic scrambling among the oxygen sites of FXeONO2 which was confirmed by factor-group analyses of the 16 isotopomeric crystallographic unit cells that result from syn-/anti-isomerization, FXe 16ON(16OA18OS)/FXe 16ON(16OS18OA), among the four FXeONO2 molecules of the unit cell. The intermediate oxide fluoride, O(XeF)2, was observed in the synthesis of FXeONO2, providing valuable insight into the reaction pathway. (Abstract shortened by UMI.);The XeOF3- anion has been synthesized as its Cs+ and N(CH3)4+ salts, and structurally characterized in the solid state by low-temperature Raman spectroscopy. The calculated anion geometry is based on a square planar AX 3YE2 VSEPR arrangement with the longest Xe--F bond trans to the oxygen atom. The F--Xe--F angle is bent away from the oxygen atom to accommodate the greater spatial requirement of the oxygen double bond domain. |
