Through the use of ab initio calculations, the possibility of formation of σ-hole interaction between ZO3 (Z=Ar, Kr and Xe) and carbene species is investigated. Since singlet carbenes show a negative electrostatic potential on their divalent carbon atom, they can favorably interact with the positive electrostatic potential generated by the σ-hole of Z atom of ZO3. The characteristic of this interaction, termed as “carbene-aerogen” bond, is analyzed in terms of geometric, interaction energies and electronic features. The energy decomposition analysis indicates that for all complexes analyzed here, the electrostatic energy is more negative than the polarization or dispersion energy term. According to the electron density analysis, some partial covalent character can be ascribed to Xe···C interactions. In addition, the carbene-aerogen bond exhibits cooperative effects with the H···O hydrogen-bonding interaction in ternary complexes where both interactions coexist. For a given carbene, the amount of these cooperative effects increases with the size of the Z atom. The results obtained in this work may be helpful for the extension and future application of σ-hole intermolecular interactions as well as coordination chemistry.
