DFT Study and NBO Analysis of Conformational Properties of 2-Substituted 2-Oxo-1,3,2-Dioxaphosphorinanes and Their Dithia and Diselena Analogs

Title:DFT Study and NBO Analysis of Conformational Properties of 2-Substituted 2-Oxo-1,3,2-Dioxaphosphorinanes and Their Dithia and Diselena Analogs

Volume: 12 Issue: 7

Author(s): Fatemeh Azarakhshi, Mehrnoosh Khaleghian and Nazanin Farhadyar

Affiliation:

Keywords: 2-Oxo-1, 3, 2-dioxaphosphorinanes, NBO, DFT, Stereoelectronic, Organophosphorus, GAE, Conformational analysis, LUMO, HOMO, Electron delocalizations, ab initio.

Abstract: The conformational behaviors of 2-fluoro-2-oxo-1,3,2- (compounds 1-3), 2-chloro-2-oxo- 1,3,2- (compounds 4-6), 2-bromo-2-oxo-1,3,2- (compounds 7-9), -dioxa, -dithia, -diselena phosphorinanes have been analyzed by means of hybrid density functional theory (B3LYP/6- 311+G**) and ab initio molecular orbital (HF/6-311+G**) based methods and NBO interpretation. The results justified the axial conformations preference of compounds 1-9. The calculated relative energies ΔE₀ and Gibbs free energy difference values (ΔGeq-ax) between the axial and equatorial conformations decrease from compound 1 to compound 3, from compound 4 to compound 6 and from compound 7 to compound 9. The NBO analysis showed the same trends for the accordingly calculated Generalized Anomeric Effect (GAE) values. The correlations between the GAE, dipole-dipole interactions, Wiberg Bond Index (WBI), orbital occupancies, HOMO, LUMO energies and structural parameters for rationalization of conformational behavior of compounds 1-9 have been investigated.

Cite this article as:

Azarakhshi Fatemeh, Khaleghian Mehrnoosh and Farhadyar Nazanin, DFT Study and NBO Analysis of Conformational Properties of 2-Substituted 2-Oxo-1,3,2-Dioxaphosphorinanes and Their Dithia and Diselena Analogs, Letters in Organic Chemistry 2015; 12 (7) . https://dx.doi.org/10.2174/1570178612666150529205707