The proton transfer process observed in the structure analysis and DFT calculations of (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol

[ X ]

Tarih

2010

Dergi Başlığı

Dergi ISSN

Cilt Başlığı

Yayıncı

Springer/Plenum Publishers

Erişim Hakkı

info:eu-repo/semantics/closedAccess

Özet

The crystal and molecular structures of an o-hydroxy Schiff base derivative, (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol, have been determined by single crystal X-ray diffraction analyses at 296 and 100 K. The results from temperature-dependent structural analysis regarding the tautomeric equilibrium of the compound were interpreted with the aid of quantum chemical calculations. To clarify the tautomerization process and its effects on the molecular geometry, the gas-phase geometry optimizations of two possible tautomers of the title molecule, its OH and NH form, were achieved using DFT calculations with B3LYP method by means of 6-31 + G(d,p) basis set. In order to describe the potential barrier belonging to the phenolic proton transfer, nonadiabatic Potential Energy Surface (PES) scan was performed based on the optimized geometry of the OH tautomeric form by varying the redundant internal coordinate, O-H bond distance. The Harmonic Oscillator Model of Aromaticity (HOMA) indices were calculated in every step of the scan process so as to express the deformation in the aromaticities of principal molecular moieties of the compound. The results show that there is a dynamic equilibrium between the aromaticity level of phenol and chelate ring and furthermore pi-electron coupling affecting overall molecule of the title compound. Charge transfer from phenol ring to pseudo-aromatic chelate ring increases with increasing temperature, whereas pi-electron transfer from chelate ring to anisole ring is decreased as temperature increases. The most strength intramolecular H-bonds are observed for conformers close to transition state.

Açıklama

Anahtar Kelimeler

Schiff base, Tautomerism, SUMP instruction, HOMA, PES scan, Crystal structure

Kaynak

Structural Chemistry

WoS Q Değeri

Q2

Scopus Q Değeri

Q2

Cilt

21

Sayı

4

Künye