Computational Study about Through-Bond and Through-Space Interactions in [2.2]Cyclophanes

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2007-03, Vol.111 (9), p.1705-1712
• Main Authors: Caramori, Giovanni F, Galembeck, Sérgio E
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp066863h

An analysis of the electron density, obtained by B3PW91/6-31+G(d,p), B3LYP/6-31+G(d,p), and MP2/6-31+G(d,p) for [2,2]cyclophanes isomers, [2.2]paracyclophane, anti-[2.2]metacyclophane, syn-[2.2]metacyclophane, and [2.2]metaparacyclophane, was made through natural bond orbitals (NBO), natural steric analysis (NSA), and atoms in molecules (AIM) methods and through analysis of frontier molecular orbitals (MOs). NBO indicates that all compounds present through-bond interactions, but only the conformers of [2.2]metacyclophane present significant through-space interactions. The last interactions are observed in AIM analysis and by the plots of MOs. AIM indicates that these through-space interactions are closed-shell ones, and they stabilize the conformers. In contrast, all isomers present through-bond and through-space repulsive interactions. In addition, the atomic properties, computed over the atomic basins, showed that the position of the bridges and the relative displacement of the rings can affect the atomic charges, the first atomic moments, and the atomic volumes.