The previously reported organoxenonium(IV) salt, [C6F5XeF2][BF4], has been synthesized in high yield and high purity for the first time by improvement of the reaction conditions of XeF4 with C6F5BF2 in CH2Cl2. This salt and the related complex salts, [C6F5XeF2][BF4]�1.5NCCH3 and [C6F5XeF2][BF4]�2HF (Figure 1), have been fully characterized in the solid state by low-temperature, single-crystal X-ray diffraction (�173 �C), and Raman spectroscopy (�160 �C). Single crystals of [C6F5XeF2][BF4] and [C6F5XeF2][BF4]�1.5NCCH3 were grown from CH3CN and CH2Cl2 mixtures whereas crystals of the HF complex were grown from anhydrous HF (aHF). In all three structures, the C6F5XeF2+ cation exhibits two strong contacts to the BF4� anion or the solvent molecules, HF and CH3CN, which result in a highly distorted pentagonal planar environments around the electrophilic Xe(IV) center. The solid-state Raman spectra of [C6F5XeF2][BF4] and isoelectronic C6F5IF2 have been assigned with the aid of quantum-chemical calculations. Improved 19F, 11B, and 129Xe NMR spectra of [C6F5XeF2][BF4] in CH3CN and aHF are reported and the long-term stabilities of these solutions have been investigated. The oxidative fluorinating properties of [C6F5XeF2][BF4] have been investigated through its reactions with Pn(C6F5)3 and (Pn = P, As, Bi) and C6F5X (X = Br, I). The reactions of C6F5BF2 with the Xe(VI) compounds, XeF6 and XeOF4, will also be discussed.

Structure and bonding in [C6F5XeF2][BF4], [C6F5XeF2][BF4]�1.5NCCH3, and [C6F5XeF2][BF4]�2HF and the reactivity of [C6F5XeF2][BF4]

248th National Meeting (2014)

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