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Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
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The elements in group 18 are noble gases (helium, neon, argon, krypton, xenon, and radon). They earned the name “noble” because they were assumed to be nonreactive since they have filled valence shells. In 1962, Dr. Neil Bartlett at the University of British Columbia proved this assumption to be false.
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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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Sulfonium cation [SF3]+ complexes with noble gases.

Mariusz Michalczyk1, Wiktor Zierkiewicz1, Pavel Hobza2

  • 1Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland. mariusz.michalczyk@pwr.edu.pl.

Physical Chemistry Chemical Physics : PCCP
|March 4, 2026
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Summary

Chalconium cations, like [SF3]+, can form stable complexes with noble gases (Ar, Kr, Xe). These interactions are weak, with electrostatic forces shifting to dispersive ones when noble gases replace ligands or anions.

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Area of Science:

  • Inorganic chemistry
  • Computational chemistry
  • Supramolecular chemistry

Background:

  • Chalconium cations are potent Lewis acids featuring hypervalent chalcogen atoms.
  • They find applications in organocatalysis and crystal engineering.

Purpose of the Study:

  • To investigate the electrophilic nature of chalconium cations.
  • To model complexes of the [SF3]+ cation with noble gas atoms.

Main Methods:

  • Computational modeling using a polarizable continuum model.
  • Synthesis and characterization of [SF3(NCCH3)2Ng]+ and [SF3(Ng)2][SbF6] complexes (Ng = Ar, Kr, Xe).

Main Results:

  • Stable tetrameric complexes with weak interaction energies (-2 to -1 kcal mol-1) were computed.
  • Replacing the [SbF4]- anion or NCCH3 ligands with noble gas atoms weakened interaction energies.
  • The nature of interaction shifted from electrostatic to dispersive upon noble gas substitution.

Conclusions:

  • Noble gas atoms can act as ligands in chalconium cation complexes.
  • The electronic environment significantly influences the bonding characteristics between chalconium cations and noble gases.