Conformational behaviors of trans-2,3- and trans-2,5-dihalo 1,4-diselenanes. A complete basis set, hybrid-density functional theory study and natural bond orbital interpretations

MOUSAVI, Seiedeh Negar
KAYI, Hakan
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Journal of Molecular Modeling
Complete basis set CBS-4, hybrid-density func tional theory (hybrid-DFT: B3LYP/6-311+G**) based methods and natural bond orbital (NBO) interpretations have been used to examine the contributions of the hyperconjugative, electrostatic, and steric effects on the con formational behaviors of trans-2,3-dihalo-1,4-diselenane [halo=F (1), Cl (2), Br (3)] and trans-2,5-dihalo-1,4- diselenane [halo = F (4), Cl (5), Br (6)]. Both levels of theory showed that the axial conformation stability, compared to its corresponding equatorial conformation, decreases from com pounds 1→3 and 4→6. Based on the results obtained from the NBO analysis, there are significant anomeric effects for compounds 1-6. The anomeric effect associated with the electron delocalization is in favor of the axial conformation and increases from compounds 1→3 and 4→6. On the other hand, dipole moment differences between the axial and equa torial conformations [Δ(μeq - μax)] decrease from compounds 1→3. Although Δ(μeq-μax) parameter decreases from com pound 1 to compound 3, the dipole moment values of the axial conformations are smaller than those of their corresponding equatorial conformations. Therefore, the anomeric effect as sociated with the electron delocalizations (for halogen-C-Se segments) and the electrostatic model associated with the dipole-dipole interactions fail to account for the increase of the equatorial conformations stability on going from com pound 1 to compound 3. Since there is no dipole moment for the axial and equatorial conformations of compounds 4-6, consequently, the conformational preferences in compounds 1-6 is in general dictated by the steric hindrance factor asso ciated with the 1,3-syn-axial repulsions. Importantly, the CBS-4 results show that the entropy difference (ΔS) between the equatorial axial conformations increases from compounds 1→3 and 4→6. This fact can be explained by the anomeric effect associated with the electron delocalization which affects the C2-Se bond orders and increase the rigidity of the corre sponding rings. The Gibbs free energy difference values be tween the axial and equatorial conformations (i.e. ΔGax-ax and ΔGeq-eq) of compounds 1 and 4, 2 and 5 and also 3 and 6 have been calculated. The correlations between the anomeric effect, electrostatic model, ΔGeq-ax, ΔGax-ax, ΔGeq-eq, bond orders, dipole-dipole interactions, structural parameters and confor mational behaviors of compounds 1-6 have been investigated.
chemical engineering