XeF Coordination Complexes of the [BrO] Cation, [OBr(FXeF)][AsF] ( = 1, 2) and [OBr(FXeF)][SbF]; Their Syntheses and Structural Characterizations.

The syntheses and structural characterizations of the first XeF coordination complexes of the [BrO] cation are described. The reactions of [BrO][PnF] (Pn = As, Sb) with XeF in anhydrous HF solvent yield the salts [OBr(FXeF)][AsF] ( = 1, 2) and [OBr(FXeF)][SbF], which were characterized by low-temperature (LT) Raman spectroscopy and single-crystal X-ray diffraction (SCXRD). The XeF ligands and [PnF] coordinate to the Lewis acidic [BrO] cation through primarily electrostatic Br---F σ-hole bonds that result from coordination of the F atoms into regions of high positive electrostatic potential on the Br(V) atom and have bond trajectories that avoid the stereoactive valence electron lone-pair of Br(V). The complexes and their structural characterizations by LT Raman spectroscopy and SCXRD significantly extend the coordination chemistry of Br(V) and provide rare examples of a noble-gas difluoride coordinated to a strong oxidant main-group Lewis acid center.