Structural, Electronic, Reactivity, and Conformational Features of 2,5,5-Trimethyl-1,3,2-diheterophosphinane-2-sulfide, and Its Derivatives: DFT, MEP, and NBO Calculations

Abstract

In this study, we used density functional theory (DFT) and natural bond orbital (NBO) analysis to determine the structural, electronic, reactivity, and conformational features of 2,5,5-trimethyl-1,3,2-di-heteroatom (X) phosphinane-2-sulfide derivatives (X = O (compound 1), S (compound 2), and Se (compound 3)). We discovered that the features improve dramatically at 6-31G** and B3LYP/6-311+G** levels. The level of theory for the molecular structure was optimized first, followed by the frontier molecular orbital theory development to assess molecular stability and reactivity. Molecular orbital calculations, such as the HOMO–LUMO energy gap and the mapping of molecular electrostatic potential surfaces (MEP), were performed similarly to DFT calculations. In addition, the electrostatic potential of the molecule was used to map the electron density on a surface. In addition to revealing molecules’ size and shape distribution, this study also shows the sites on the surface where molecules are most chemically reactive.

Sulfur Centered Hydrogen Bonding in Thioglycolic Acid and Its Clusters: A Computational Exploration

“…Therefore, gaining precise knowledge about the conformational aspects of a molecule becomes crucial. Conformational analysis not only provides insights into the molecule’s structural flexibility but also allows for the identification of the relationship between conformational flexibility and reactivity. − In 1995, Yamaguchi et al measured the microwave spectra of TGA and concluded therefrom that the mercapto-H group is involved in weak intramolecular hydrogen bonding, potentially allowing peripheral atoms to tunnel through low potential barriers associated with the twisting of C–S and C–C bonds . Subsequently, Caminati et al employed the free jet technique to reassign the rotational spectrum of TGA after observing significantly notable variations in the spectroscopic parameters between the two states of TGA previously reported by Yamaguchi et al In 2002, Fantoni et al conducted computational investigations utilizing various ab initio methods to analyze the conformation and S–H inversion barrier of TGA.…”