Aromaticity balance, pi-electron cooperativity and H-bonding properties in tautomerism of salicylideneaniline: the quantum theory of atoms in molecules (QTAIM) approach

作者：Karabiyik Hasan^*; Sevincek Resul; Petek Hande; Aygun Muhittin

来源：Journal of Molecular Modeling, 2011, 17(6): 1295-1309.

DOI：10.1007/s00894-010-0832-3

• Aromaticity
• Hypervalent
• Hypovalent
• Intramolecular electron transfer
• Para delocalization index
• Schiff base

Topological analysis based on DFT calculations regarding proton transfer reaction in salicylideneaniline (SA) was performed to scrutinize possible changes in the intramolecular H-bond, pi-electron delocalization and aromaticity levels of certain fragments. Quantum chemical calculations and natural bond orbital (NBO) analyses were carried out over a tautomeric ensemble whose members correspond to the molecules at different stages in tautomeric interconversion of SA. The elaboration of intramolecular hydrogen bonding in terms of the relevant topological parameters and the interpretation of certain dependencies regarding its strength were examined. The results show that delocalization index (DI) between donor and acceptor atom delta(O,N) is a useful topological parameter for describing H-bond strength, which is influenced by pi-delocalization level within quasiaromatic chelate ring, indicating its resonance-assisted character. NBO analyses reveal that lone-pair (LP) population on N center also affects the strength of intramolecular H-bond in SA. Furthermore, pi-electron transfer accompanying intramolecular proton migration in SA is brought into being through formally vacant non-Lewis type LP* orbital on the tautomeric proton. As a result of this, tautomeric protons in molecular entities near TS have hypovalent character due to the lack of electron population in the bonding orbital relative to that in LP* orbital. While H-bonds in the tautomeric ensemble of SA are predominantly partial covalent, molecular entities close to transition state have the strongest covalent H-bonds. The most important result is also that there are linear correlations between the orders of bonds (hydroxyl and amine) involving intramolecular H-bond and electron density values at the relevant BCPs due to partially covalent character of these bonds, contrary to exponential behavior as for purely covalent bonds. Quasiaromatic chelate ring formation is established not only to compel a reduced aromaticity of salicylidene ring but also to decrease in LP-population on N.

• 出版日期2011-6