XeOF<sub>2</sub>, F<sub>2</sub>OXeN≡CCH<sub>3</sub>, and XeOF<sub>2</sub>·<i>n</i>HF:  Rare Examples of Xe(IV) Oxide Fluorides David S. Brock Vural Bilir Hélène P. A. Mercier Gary J. Schrobilgen 10.1021/ja0673480.s002 https://acs.figshare.com/articles/journal_contribution/XeOF_sub_2_sub_F_sub_2_sub_OXeN_CCH_sub_3_sub_and_XeOF_sub_2_sub_i_n_i_HF_Rare_Examples_of_Xe_IV_Oxide_Fluorides/3016621 The syntheses of XeOF<sub>2</sub>, F<sub>2</sub>OXeN⋮CCH<sub>3</sub>, and XeOF<sub>2</sub>·<i>n</i>HF and their structural characterizations are described in this study. All three compounds are explosive at temperatures approaching 0 °C. Although XeOF<sub>2</sub> had been previously reported, it had not been isolated as a pure compound. Xenon oxide difluoride has now been characterized in CH<sub>3</sub>CN solution by <sup>19</sup>F, <sup>17</sup>O, and <sup>129</sup>Xe NMR spectroscopy. The solid-state Raman spectra of XeOF<sub>2</sub>, F<sub>2</sub>OXeN⋮CCH<sub>3</sub>, and XeOF<sub>2</sub>·<i>n</i>HF have been assigned with the aid of <sup>16</sup>O/<sup>18</sup>O and <sup>1</sup>H/<sup>2</sup>H enrichment studies and electronic structure calculations. In the solid state, the structure of XeOF<sub>2</sub> is a weakly associated, planar monomer, ruling out previous speculation that it may possess a polymeric chain structure. The geometry of XeOF<sub>2</sub> is consistent with a trigonal bipyramidal, AX<sub>2</sub>YE<sub>2</sub>, VSEPR arrangement that gives rise to a T-shaped geometry in which the two free valence electron lone pairs and Xe−O bond domain occupy the trigonal plane and the Xe−F bond domains are trans to one another and perpendicular to the trigonal plane. Quantum mechanical calculations and the Raman spectra of XeOF<sub>2</sub>·<i>n</i>HF indicate that the structure likely contains a single HF molecule that is H-bonded to oxygen and also weakly F-coordinated to xenon. The low-temperature (−173 °C) X-ray crystal structure of F<sub>2</sub>OXeN⋮CCH<sub>3</sub> reveals a long Xe−N bond trans to the Xe−O bond and a geometrical arrangement about xenon in which the atoms directly bonded to xenon are coplanar and CH<sub>3</sub>C⋮N acts as a fourth ligand in the equatorial plane. The two fluorine atoms are displaced away from the oxygen atom toward the Xe−N bond. The structure contains two sets of crystallographically distinct F<sub>2</sub>OXeN⋮CCH<sub>3</sub> molecules in which the bent Xe−N−C moiety lies either in or out of the XeOF<sub>2</sub> plane. The geometry about xenon is consistent with an AX<sub>2</sub>YZE<sub>2</sub> VSEPR arrangement of bond pairs and electron lone pairs and represents a rare example of a Xe(IV)−N bond. 2007-03-28 00:00:00 F 2OXeN molecules Xenon oxide difluoride AX 2YE VSEPR arrangement XeOF 2 plane Raman spectra CH 3CN solution bond 129 Xe NMR spectroscopy HF CH 3C acts AX 2YZE VSEPR arrangement XeOF 2 xenon