Nature of the interaction between ammonia derivatives and carbon disulfide. A theoretical investigation

Abstract

AbstractThe interactions between NH3, its methylated and chlorinated derivatives and CS2 are investigated by ab initio CCSD(T) and density functional BLYP‐D3 methods. The CCSD(T)/aug‐cc‐pVTZ calculated interaction energies of complexes characterized by the S···N chalcogen bonds range between −1.71 and −2.78 kcal mol−1. The S···N bonds are studied by atoms in molecules, natural bond orbital, and noncovalent interaction methods. The lack of correlation between the interaction energies of methylated amines complexes and the electrostatic potential results from the lone pair effect in aliphatic amines. Different structures of CS2 complexed with ammonia derivatives, stabilized by other than the S···N chalcogen bonds, are also predicted. These structures are characterized by interaction energies ranging between 1.15 and 3.46 kcal mol−1. The results show that the complexing ability of CS2 is not very high but this molecule is able to attack the electrophilic or nucleophilic sites of a guest molecule.