Theoretical Aspects of Organoselenium Chemistry

Abstract

The chapter offers an overview of the applications of theoretical methods in the area of organoselenium chemistry. In recent years, the availability of reliable basis sets and computational methods, especially the emergence of density functional methods, have enabled studies on increasingly complex chemical problems. A plethora of such problems in organoselenium chemistry and interesting insights on structure, properties, and reactions derived by using computational methods constitute the contents of this chapter. The types of situations described range from exotic briefly lived intermediates to structural and electronic features of stable and crystalline molecules. Properties such as nuclear magnetic resonance chemical shift and the comparison between computed and experimental quantities have been provided extensively. A number of reactions of selenium compounds with emphasis on biologically significant reactions have been highlighted. In particular, computational studies on glutathione peroxidate activity of selenium compounds have been elaborated. The electronic origins of inter‐ and intra‐molecular nonbonding interactions in organoselenium compounds and an illustration of how theoretical methods have been vital in quantifying such weak interactions have been provided.

Nearest-Neighbor and Non-Nearest-Neighbor Interactions between Substituents in the Benzene Ring. Experimental and Theoretical Study of Functionally Substituted Benzamides

“…The concept of substituent effects in the benzene ring is not straightforward, but it is successfully realized in organic and inorganic chemistry. 2 Also in thermochemistry, pairwise nearest-neighbor and non-nearestneighbor interactions between substituents in the benzene ring are also responsible for the distribution of the ortho-, meta-, and para-isomers, e.g., in the case of production of the industrially important antioxidant p-tert-butylphenol via alkylation of phenol with isobutene. 3 Moreover, knowledge about pairwise interactions in the benzene ring is essential for prediction of thermochemical properties of the benzene derivatives based on the group-additivity procedure.…”

“…Numerically, the substituent effects are often described by various constants related to the substituents X and Y, which are generally divided into electron-withdrawing and electron-donating groups. The concept of substituent effects in the benzene ring is not straightforward, but it is successfully realized in organic and inorganic chemistry . Also in thermochemistry , pairwise nearest-neighbor and non-nearest-neighbor interactions between substituents in the benzene ring are also responsible for the distribution of the ortho -, meta -, and para -isomers, e.g., in the case of production of the industrially important antioxidant p - tert -butylphenol via alkylation of phenol with isobutene .…”