title: 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.
abstract: Complete basis set CBS-4, hybrid-density functional 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 conformational 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 compounds 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 equatorial conformations [Δ(μ(eq)-μ(ax)] decrease from compounds 1 → 3. Although Δ(μ(eq)-μ(ax)) parameter decreases from compound 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 associated 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 compound 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 associated with the 1,3-syn-axial repulsions. Importantly, the CBS-4 results show that the entropy difference (∆S) 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 corresponding rings. The Gibbs free energy difference values between the axial and equatorial conformations (i.e. ΔG(ax-ax) and ΔG(eq-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, ΔG(eq-ax), ΔG(ax-ax), ΔG(eq-eq), bond orders, dipole-dipole interactions, structural parameters and conformational behaviors of compounds 1-6 have been investigated.
authors.affiliation: Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran, nori_ir@yahoo.com.
authors.forename: Davood
authors.initials: D
authors.lastname: Nori-Shargh
authors.forename: Seiedeh Negar
authors.initials: SN
authors.lastname: Mousavi
authors.forename: Hakan
authors.initials: H
authors.lastname: Kayi
mesh_terms: D003198:Computer Simulation; D004735:Energy Transfer; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D016566:Organoselenium Compounds / Q000737:chemistry*; D055672:Static Electricity; D013329:Structure-Activity Relationship
chemical_list: D016566:Organoselenium Compounds