Aromatization of triafulvene and its exocyclic Si, Ge, and Sn derivations by complexation with halogen atoms

Abstract

The geometries of triafulvene (TF) and its exocyclic Si, Ge, and Sn analogues complexes with F, Cl, Br, and I halogen atoms (TF(X)Y, XC, Si, Ge, and Sn; YF, Cl, Br, and I) were studied. The complexes were optimized at DFT(B3LYP)/6-311+G(d,p) level of theory. To assess the aromaticity of the considered complexes the geometry-based (HOMA), magnetism-based (NICS), and recently introduced electronic-based (electric field gradient (EFG(0); Shannon aromaticity (SA)) aromaticity indices were employed. The increasing tendency of aromaticity in each complex species was noted as the series of TF(X)F > TF(X)Cl > TF(X)Br > TF((X)I. Then, the binding energies corrected by basis set super position error (BSSE) were calculated by single point energy calculations at M06-2X/6-311+G(d,p) level. Natural bond orbital (NBO) analysis confirmed that the charge transfer takes place from TF(X) to the halogen atoms. Some topological parameters, within the framework of the quantum theory of atoms in molecules (QTAIM), were also calculated to estimate the aromaticity of the complexes. It was seen that there are some important correlations between the topological parameters and aromaticity indices. In addition the most striking finding was that all the TF(X) molecules are connected with the halogen atoms through YC1C2 () noncovalent interaction. This interaction was also investigated through noncovalent interaction (NCI) analysis.