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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

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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.

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Acknowledgments

We thank Dr. Daryoush Tahmasebi for CBS-4 calculations.

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Authors and Affiliations

  1. Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran

    Davood Nori-Shargh & Seiedeh Negar Mousavi

  2. Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry, The University of Texas, Austin, TX, 78712, USA

    Davood Nori-Shargh

  3. Department of Chemical Engineering and Applied Chemistry, Atilim University, Ankara, 06836, Turkey

    Hakan Kayi

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  1. Davood Nori-Shargh
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  2. Seiedeh Negar Mousavi
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  3. Hakan Kayi
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Correspondence to Davood Nori-Shargh or Hakan Kayi.

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Dedicated to the memory of Professor James E. Boggs

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Nori-Shargh, D., Mousavi, S.N. & Kayi, H. 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. J Mol Model 20, 2249 (2014). https://doi.org/10.1007/s00894-014-2249-x

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