Over the past decade, significant advances have been made in the field of Xe(IV) chemistry. High-yield syntheses of high-purity XeOF2, F2OXeN=CCH3, and XeOF2�nHF will be described along with their full characterizations by Raman and NMR spectroscopy. Quantum-chemical calculations indicate that all three compounds are endothermic and display shock sensitivity. The X-ray crystal structure of F2OXeN=CCH3has been determined, documenting the first example of a Xe(IV)-N bond. Xenon oxide difluoride has also provided a route to several new Xe(IV) oxide fluoride species. The Lewis acid/base properties of XeOF2 have led to the syntheses and characterizations of the H(OXeF2)n+ and FXe(OXeF2)n+ cations, as their AsF6- salts, and the XeOF3- anion [figure 1b], as its N(CH3)4+ and Cs+ salts. The HOXeF2+ cation [figure 1c] is the first hydroxy derivative of xenon to have been structurally characterized, whereas FXeOXeF2+ provides the first example of a Xe(II)/Xe(IV) mixed oxidation state cation and a Xe(II)-O-Xe(IV) bridge. The XeOF3- anion is also of interest because it is presently the only example of an AX3YE2VSEPR arrangement.The missing Xe(IV) oxide, XeO2, has been synthesized at 0 oC by hydrolysis of XeF4 in water and in 2.00 M H2SO4(aq), and characterized by low-temperature Raman spectroscopy.

Advances in the oxide and oxide fluoride chemistry of xenon (IV)

248th National Meeting (2014)

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