Xenon Trioxide Adducts of O‐Donor Ligands; [(CH3)2CO]3XeO3, [(CH3)2SO]3(XeO3)2, (C5H5NO)3(XeO3)2, and [(C6H5)3PO]2XeO3Journal Articles
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AbstractXenon trioxide (XeO3) forms adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine‐N‐oxide, and acetone by coordination of the ligand oxygen atoms to the XeVI atom of XeO3. 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, solid (C5H5NO)3(XeO3)2, [(C6H5)3PO]2XeO3, and [(CH3)2SO]3(XeO3)2 are insensitive to mechanical shock. The [(CH3)2SO]3(XeO3)2 adduct slowly decomposes over several days to (CH3)2SO2, Xe, and O2. All three complexes undergo rapid deflagration when ignited by a flame. Both [(C6H5)3PO]2XeO3 and (C5H5NO)3(XeO3)2 are room‐temperature stable and the [(CH3)2CO]3XeO3 complex dissociates at room temperature to form a stable solution of XeO3 in acetone. The xenon coordination sphere of [(C6H5)3PO]2XeO3, a distorted square‐pyramid, provides the first example of a five‐coordinate XeO3 complex with only two Xe‐ ‐ ‐O adduct bonds. The xenon coordination spheres of the remaining adducts are distorted octahedra, comprised of three Xe‐ ‐ ‐O secondary bonds that are approximately trans to the primary Xe−O bonds of XeO3. Quantum‐chemical calculations were used to assess the nature of the Xe‐ ‐ ‐O adduct bonds, which are described as predominantly electrostatic bonds between the nucleophilic oxygen atoms of the bases and the σ‐holes of the electrophilic xenon atoms.
