An ab initio study on properties of cationic chalcogen bonds in XF₂Y⁺⋯NCZ (X═H, CN, F; Y═S, Se; Z═H, Cl, Br) complexes

ABSTRACT

The geometries, interaction energies, and bonding properties of cationic chalcogen bonds are studied in binary complexes XF₂Y⁺⋯NCZ (X═H, CN, F; Y═S, Se; Z═H, Cl, Br). The nature of these interactions is studied by a vast number of methods, including molecular electrostatic potential (MEP), Noncovalent Interaction Index (NCI), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO) analyses. The interaction energies of these complexes vary between −20.94 kcal/mol in HF₂S⁺⋯NCH and −33.72 kcal/mol in F₃Se⁺⋯NCBr. According to the QTAIM analysis, all these cationic chalcogen bonds are classified as a closed-shell interaction with a partial covalent character. Moreover, cooperative effects between cationic chalcogen bond and hydrogen or halogen bond interactions are studied in ternary XF₂Y⁺⋯NCZ⋯NH₃ complexes. These cooperative effects are analyzed in terms of the parameters derived from the QTAIM and NBO analyses, and electron density difference plots.

GRAPHICAL ABSTRACT

KEYWORDS:

• Chalcogen bond
• cooperativity
• NBO
• QTAIM
• electrostatic potential

Disclosure statement

No potential conflict of interest was reported by the authors.