Through-Bond and Through-Space Interactions in [2,2]Cyclophanes
AUTOR(ES)
Galembeck, Sérgio E.; Orenha, Renato P.; Madeira, Rafael M.; Peixoto, Letícia B.; Parreira, Renato L. T.
FONTE
J. Braz. Chem. Soc.
DATA DE PUBLICAÇÃO
2021-07
RESUMO
The interpretation of the distortions of the electron distribution in [2,2]cyclophanes (22-CPs) is controversial. Some studies indicate that there is an accumulation of electron density (ρ) outside the cavity of 22-CPs. The nature of through-space (ts) interaction is still under debate. The relative importance of ts and through-bond (tb) is an open question. In an attempt to clarify these points, we have investigated five 22-CPs and their corresponding toluene dimers by molecular orbitals analysis, electron density difference analysis, some topological analysis of ρ (quantum theory of atoms in molecules (QTAIM), electron localization function (ELF) and noncovalent interactions (NCI)), and energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV). ρ is concentrated inside the inter-ring region. All the analyses indicated that ts is predominant. The ts is composed by attractive dispersion and Pauli repulsion, with a small covalent contribution. Except for 1 and 6, all the compounds present inter-ring bond paths.
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