Xenon Trioxide Adducts of O ‐Donor Ligands; [(CH 3 ) 2 CO] 3 XeO 3 , [(CH 3 ) 2 SO] 3 (XeO 3 ) 2 , (C 5 H 5 NO) 3 (XeO 3 ) 2 , and [(C 6 H 5 ) 3 PO] 2 XeO 3 Academic Article uri icon

  •  
  • Overview
  •  
  • Research
  •  
  • Identity
  •  
  • Additional Document Info
  •  
  • View All
  •  

abstract

  • Xenon 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 (C5 H5 NO)3 (XeO3 )2 , [(C6 H5 )3 PO]2 XeO3 , and [(CH3 )2 SO]3 (XeO3 )2 are insensitive to mechanical shock. The [(CH3 )2 SO]3 (XeO3 )2 adduct slowly decomposes over several days to (CH3 )2 SO2 , Xe, and O2 . All three complexes undergo rapid deflagration when ignited by a flame. Both [(C6 H5 )3 PO]2 XeO3 and (C5 H5 NO)3 (XeO3 )2 are room-temperature stable and the [(CH3 )2 CO]3 XeO3 complex dissociates at room temperature to form a stable solution of XeO3 in acetone. The xenon coordination sphere of [(C6 H5 )3 PO]2 XeO3 , 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.

authors

publication date

  • September 20, 2019