Hybrid-DFT study and NBO interpretations of conformational behaviors of 2-methoxy-1,2,4,5-tetrahydro-benzo[d]oxepine, -thiepine and -selenepine

Subject Areas : Journal of the Iranian Chemical Research

Davood Nori-Shargh ¹ , Sogand Sarikhani ² , Hooriye Yahyaei ³ , Seiedeh Negar Mousavi ⁴ , Nasrin Masnabadi ⁵

1 - Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran
2 - Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran
3 - Department of Chemistry, Zanjan Branch, Islamic Azad University, Zanjan, Iran
4 - Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran
5 - Department of Chemistry, Roudehen Branch, Islamic Azad University, Roudehen, Iran

Received: 2011-02-10 Accepted : 2011-02-28 Published : 2011-03-20

Keywords: anomeric effects, Molecular modeling, Ab initio, NBO, Tereoelectronic interactions, Tetrahydro-benzo[d]oxepine,

Abstract :

NBO analysis and density functional theory (DFT: B3LYP/6-311+G**) based method were used to study the impacts of the anomeric effects (AE) on the conformational properties of 2-methoxy-1,2,4,5-tetrahydro-benzo[d]oxepine (1), -thiepine (2) and -selenepine (3). The Gibbs free energy difference (Geq–Gax) values (i.e. ΔGeq-ax) at 298.15 K and 1 atm between the axial and equatorial conformations increase from compound 1 to compound 2 but decrease from compound 2 to compound 3. The NBO analysis showed that the AE associated with donor-acceptor (LP→σ*) interactions increases from compound 1 to compound 2 but decreases from compound 2 to compound 3. Also, the calculated dipole moment difference [Δ(μeq - μax)] values between the axial and equatorial conformations increase from compound 1 to compound 2 but increase from compound 2 to compound 3. Based on the results obtained, there is no conflict between the AE and the electrostatic interactions [i.e. Δ(μeq - μax)] on the conformational behaviors of compounds 1-3.

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