Tautomerism in Xenon Hexafluoride: An Investigation of Xenon Hexafluoride and its Complexes by Raman Spectroscopy

Abstract

Raman spectra are reported for (i) complexes of xenon hexafluoride with the fluoride‐ion acceptors BF3, PdF4, PF5, AsF5, RuF5, PtF5, and AuF5, and (ii) for solutions of xenon hexafluoride in HF and in WF6. Vibrational assignments are made for the cations XeF+5 and Xe2F+11, and evoke a normal coordinate analysis for XeF+5. Xenon hexafluoride, present in concentrated solution in HF as [XeF+5F−]4, progressively ionizes on dilution to give Xe2F+11; and XeF+5; on the other hand, in WF6 solution [XeF+5F−]4 exists in equilibrium only with molecular XeF6.

Single-crystal structure determination of NO2SbF6, XeF5SbF6 and XeF5Sb2F11

“…In some reviews [XeF 5 ] + [PdF 6 ] À with Pd(V) is mentioned [13][14][15]. However, this must be a typographical error, since an inspection of the original literature shows that in reality [XeF 5 ] 2 + [PdF 6 ] 2À with Pd(IV) was reported [16,17]. In contrast to the XeF 5 MF 6 phases (XeF 6 :MF 5 = 1:1) there are only two compounds known with a 1:2 ratio (i.e., XeF 5 M 2 F 11 ).…”

Crystal Growth and Characterization of the Mixed‐Cation Rb+/[XeF5]+ and Cs+/[XeF5]+ Salts

“…Only the starting materials KBF 4 and [XeF 5 ][SbF 6 ] were recovered after crystallization in the aHF solution. During the reaction between CsBF 4 and [XeF 5 ][SbF 6 ], a metathetical reaction occurred, leading to [XeF 5 ][BF 4 ] and CsSbF 6 [Equation ]. The latter reacts further with the starting material [XeF 5 ][SbF 6 ], yielding Cs[XeF 5 ][SbF 6 ] 2 [Equation ]. …”

“…The other four crystallographically equivalent F2 atoms of the [XeF 5 ] + cation occupy 8 i positions, resulting in four identical Xe–F eq bonds. The XeF 5 units have well‐known, slightly distorted pseudo‐octahedral symmetry, where the axial Xe–F ax distance [Xe1–F1: 1.790(5) Å] is slightly shorter than the equatorial [4 × Xe1–F2 eq : 1.823(2) Å]. Each [XeF 5 ] + cation makes further secondary bonds (Figure ) with one F4 fluorine atom from each of the four different [SbF 6 ] – anions [4 × Xe1 ··· F4 = 2.752(3) Å].…”

“…In 1978, Adams and Bartlett reported the growth of single crystals of XeF 6 ·BF 3 by vacuum sublimation. [7] The [XeF 5 ][BF 4 ] compound has been reported to crystallize in the orthorhombic crystal system with lattice parameters a = 8.41(2) Å, b = 8.60(2) Å, c = 17.47(4) Å, and Z = 8. [7] Their crystal data were obtained from precession photographs, where during the measurement, a single crystal of XeF 6 ·BF 3 decomposed in the beam.…”

Vibrational spectra and structural features of noble gas fluorides in cryogenic and nonaqueous solutions

“…In the Raman spectra of solutions of XeF 6 in anhydrous HF, bands with maxima at 660, 620, and 600 era -1 were detected, l,a7 Previously, 87 Thus, the processes occurring in the XeF6--HF system can be described by reactions (36) and (37). This assumption is in line with the data I on the electrical conductivity of solutions of XeF6 in HF and also with the results of NMR studies 59,75 of the XeFr--HF system.…”