A molecular orbital theory of reactivity in aromatic hydrocarbons

Abstract

In the search for a quantitative correlation between reactivity and electronic configuration of aromatic hydrocarbons, the electron density, at each carbon atom, of the highest occupied π-orbital in the ground state of the molecule is calculated by means of the LCAO method. Comparing the result of such a calculation on fifteen condensed aromatic hydrocarbons with their chemical reactivities, we find that the position at which the electron density is largest is most readily attacked by electrophilic or oxidizing reagents. It is, therefore, concluded that distinct from other π-electrons the pair of π-electrons occupying the highest orbital, which is referred to as frontier electrons, plays a decisive role in chemical activation of these hydrocarbon molecules. The theoretical significance of this discrimination of the frontier electrons in relation to the chemical activation is discussed.