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submitted on 15.09.2018 and posted on 18.09.2018by Katherine Marczenko, James Goettel, Gary Schrobilgen
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,
adducts are insensitive to mechanical shock, but undergo rapid deflagration
when ignited by a flame. Both [(C6H5)3PO]2XeO3
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
the nucleophilic oxygen atoms of the bases and the σ-holes
of the xenon atoms.