Main-Group Metal Complexes of Benzene: Predicted Features of Stabilization and Isomerization

Abstract

Complexes of metal atoms with organic molecules represent a broad variety of systems with many important applications, e.g., in metal–organic interfaces and organometallic chemistry. One class involves aromatic species like benzene (Bz). Here, such complexes with second-group metals are investigated systematically in terms of structure and shape, stability and isomerization, charge distribution and aromaticity, and polarity and IR spectra. Three groups of isomers are identified, varying from metastable to stable ones, in effect featuring “physisorption” or “chemisorption”. In particular, the high polarity of binary complexes and nonadditive stabilization of ternary systems for some isomers are found. Also, the Bz component’s shape alteration for different isomers and system sizes and related aromaticity variations are predicted to be considerable. Property evolution for the series of metal components is analyzed.

Metalloid–Organic Intermolecular Complexes with Charge State-Controlled Conformations

“…Basis set superposition error (BSSE) corrections have been applied via a conventional counterpoise technique [17]. In particular, previous calculations of identical accuracy for (composition-analogous) main-group-metal/benzene complexes [18] showed a very close match to corresponding results produced at a (more accurate) CCSD-T level. In addition, the most relevant (B-C) interactions are obviously involved in the BC diatom, which has been characterized and tested thoroughly against experimental data previously [5].…”