Xenon Trioxide Adducts of O-Donor Ligands; [(CH3)2CO]3XeO3, [(CH3)2SO]3(XeO3)2, (C5H5NO)3(XeO3)2, and [(C6H5)3PO]2XeO3

Oxygen coordination to the Xe(VI) atom of XeO3 was observed in its adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine-N-oxide, and acetone. The crystalline adducts were characterized by low-temperature, single-crystal X-ray diffraction and Raman spectroscopy. Unlike solid XeO3, which detonates when mechanically or thermally shocked, the solid [(C6H5)3PO]2XeO3, [(CH3)2SO]3(XeO3)2, and (C5H5NO)3(XeO3)2 adducts are insensitive to mechanical shock, but undergo rapid deflagration when ignited by a flame. Both [(C6H5)3PO]2XeO3 and (C5H5NO)3(XeO3)2 are air-stable whereas [(CH3)2SO]3(XeO3)2 slowly decomposes over several days and [(CH3)2CO]3XeO3 undergoes adduct dissociation at room temperature. The xenon coordination sphere of [(C6H5)3PO]2XeO3 is a distorted square pyramid which provides the first example of a five-coordinate XeO3 adduct. The xenon coordination spheres of the remaining adducts are distorted octahedra comprised of three Xe---O secondary contacts that are approximately trans to the primary Xe–O bonds of XeO3. Quantum-chemical calculations were used to assess the Xe---O adduct bonds, which are predominantly electrostatic σ-hole bonds between the nucleophilic oxygen atoms of the bases and the σ-holes of the xenon atoms.