Dual functions of Lewis acid and base of Se in F2C=Se and their interplay in F2CSe•••NH3•••HX

Abstract

High-level quantum chemical calculations of the ternary systems F2CSe∙∙∙NH3∙∙∙HX (X=BeH, BH2, OH, CN, OCH3, Cl, and F) and the corresponding binary systems have been carried out in view of geometries, vibrational frequencies, interaction energies, orbital interactions, and electron densities. The molecular electrostatic potentials of F2CSe demonstrate that the Se atom could play a dual role of Lewis acid and base to form a chalcogen bond with NH3 and a hydrogen bond or a covalent interaction with HX, respectively. The chalcogen bond can compete with the hydrogen bond for the complexes involving F2CSe, but the covalent interaction is far stronger than the chalcogen bond. In the ternary complexes, both types of interactions are strengthened by each other, characterized by a shorter binding distance, a larger electron density, and a stronger orbital interaction. The covalent interaction has a greater enhancing effect on the chalcogen bond than the hydrogen bond does, resulting in a prominent shortening of ~0.23Å distance for the Se∙∙∙N distance in F2CSe∙∙∙NH3∙∙∙BH3. The enhancement of both interactions in the ternary complexes has been understood with the electrostatic potentials and orbital interactions. Graphical Abstract The dual functions of Lewis acid and base of Se in F2CSe are enhanced each other in the ternary complexes.