Hybrid-DFT study and NBO interpretations of the conformational behavior of 1,2-dihalodisilanes

Authors

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

2 Department of Chemistry, Zanjan Branch, Islamic Azad University, Zanjan, Iran

Abstract

Hybrid-density functional theory (B3LYP/Def2-TZVPP) based method and NBO
interpretation were used to investigate the conformational behavior of 1,2-dihalodisilanes
[halo=F (1), Cl (2), Br (3), I (4)]. The B3LYP/Def2-TZVPP results showed that the anti
conformations of compounds 1-4 are more stable than their corresponding gauche
conformations. The stability of the anti conformation compared to the gauche conformation
increases from compound 1 to compound 4. The NBO analysis of donor-acceptor interactions
showed that the generalized anomeric effect (GAE) is in favor of the gauche conformations of
compounds 1 and 2. Contrary to compounds 1 and 2, GAE is in favor of the anti conformations
of compounds 3 and 4. The GAE values calculated (i.e. GAEanti-GAEgauche) increase from
compound 1 to compound 4. On the other hand, the calculated dipole moment values for the
gauche conformations increase from compound 1 to compound 3 but decreases from compound
3 to compound 4. Based on the results obtained, there is no conflict between the GAE and the
electrostatic model impacts on the conformational preferences in compounds 1-3 but the
electrostatic model can not rationalize the increase of the instability of the gauche conformation
of compound 4 compared to its anti conformation on going from compound 3 to compound 4.
Consequently, in the conflict between the GAE and the electrostatic model, the former succeeded
in accounting for the increase of the anti conformation stability from compound 1 to compound
4. There is a direct correlation between the calculated GAE, Δ[rSi-Si(G)-rSi-Si(A)] parameters. The
correlations between the GAE, bond orders, ΔGAnti-Gauche, ΔG‡(Gauche→Gauche′, C2v),
ΔG‡(Anti→Gauche, C2), dipole-dipole interactions, structural parameters and conformational
behaviors of compounds 1-4 have been investigated.

Keywords


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