DFT study on tautomerism and natural bond orbital analysis of 4-substituted 1,2,4-triazole and its derivatives: solvation and substituent effects.

Density functional theory investigations at the DFT-B3LYP/6-311++G** theoretical level employed to determine the tautomerism, substituent effects of 4-substituted 4-amino-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione, and its derivatives (4-R-H, 4-R-CH3, 4-R-F, 4-R-NO2) in the selected solvent (acetone, acetonitrile, and dichloromethane) and gas phases using the polarizable continuum method (PCM) model. The substituted 1,2,4-triazoles have two main different tautomers namely N2-H and S7-H. For considered derivatives, thione forms are more energetically stable and dominant form in the studied solvent and gas phases. In addition, geometrical parameters, charges on atoms, dipole moments, energetic properties, and the nucleus-independent chemical shifts (NICS) are investigated. It has been seen that these molecular features of the studied compound and its derivatives are mostly solvent dependent. For electron-releasing and -withdrawing derivatives in the solution and gas phases, 2-H forms are the more stable and dominant form. The relative stability of the C4-substituted 1,2,4-triazole tautomerism is influenced by the possibility for intramolecular interactions between substituent and electron-donor or electron-acceptor centers of the triazole ring.