Preparation and Raman spectra of XeOF₂, XeOF₃^–, and XeO₂F₃^–

Abstract

The preparations of XeOF,, Cs+XeOF,-, and interpreted to provide information concerning the Cs+XeO,F,-are described and Raman spectra are structures of these new oxyfluoro-species.

Fluoride Ion Donor Properties of TcO2F3and ReO2F3: X-ray Crystal Structures of MO2F3·SbF5(M = Tc, Re) and TcO2F3·XeO2F2and Raman and NMR Spectroscopic Characterization of MO2F3·PnF5(Pn = As, Sb), [ReO2F2(CH3CN)2][SbF6], and [Re2O4F5][Sb2F11]

“…Although the ν s (XeO 2 ) stretches show no consistent trend, the symmetric and antisymmetric Xe-F stretches at 499 and 553 cm -1 for the adduct display significant shifts to lower frequency relative to those of solid XeO 2 F 2 (537 and 578 cm -1 ) and matrix-isolated XeO 2 F 2 (537 and 585 cm -1 ) that likely arise from Xe‚‚‚F interactions in the adduct. The stretching frequencies for XeO 2 F 2 in the adduct are generally intermediate between those of pure XeO 2 F 2 and the XeO 2 F 3anion 58,59 and reflect the more polar nature of the XeO 2 F 2 bonding in the adduct and the Lewis acid behavior of XeO 2 F 2 toward TcO 2 F 3 in this adduct; they are also consistent with Tc-F‚‚‚Xe secondary interactions found in the crystal structure of TcO 2 F 3 ‚XeO 2 F 2 .…”

[H(OXeF2)n][AsF6] and [FXeII(OXeIVF2)n][AsF6] (n = 1, 2): Examples of Xenon(IV) Hydroxide Fluoride and Oxide Fluoride Cations and the Crystal Structures of [F3Xe---FH][Sb2F11] and [H5F4][SbF6]·2[F3Xe---FH][Sb2F11]

“…Incomplete solvation (i.e., a mixture of XeOF 2 · n HF and XeOF 2 ) resulted in extensive decomposition to [XeF][AsF 6 ] upon AsF 5 addition. The observation of XeF + suggests that the reaction likely proceeds through the formation of the unstable XeOF + cation (eq ), which decomposes to O 2 and XeF + (eq ): XeOF 2 + AsF 5 → − 78 .25em ° normalC HF [ XeOF ] [ AsF 6 ] false( normals false) false[ XeOF false] false[ AsF 6 false] ( s ) → − 78 ° C HF false[ XeF false] [ AsF 6 ] ( s ) + 1 2 O 2 false( normalg false) This reaction pathway is also consistent with the large negative Δ G 194.15 value of eq (−312.2 kJ mol –1 , Table ) obtained from a Born–Fajans–Haber thermochemical cycle using available experimental and calculated thermodynamic parameters and values derived from volume-based thermodynamics. − The calculated exothermicity is also consistent with the explosive nature of solid XeOF 2 when it reacts with liquid AsF 5 at −78 °C …”

Reactive p-block cations stabilized by weakly coordinating anions

“…Only two different fluorine-containing cations are known ([KrF] + and [Kr 2 F 3 ] + ) and some nitrile complexes, which can be described as Kr–N compounds. [KrF] + is a very strong oxidative fluorinating reagent 682 and made is possible to synthesize [XeF 5 ] + from Xe, 683 [ClF 6 ] + from ClF 5 , 684 [BrF 6 ] + from BrF 5 685 and [O 2 ] + from O 2 . 686 There are only seven crystal structures of krypton cations in the literature and five of them with the classical [AsF 6 ] – and [SbF 6 ] – anions.…”