The polarisation and charge-transfer (PCT) theoretical model for the prediction and the interpretation of the relationship between reactivity and selectivity

Abstract

A new theoretical model is presented for predicting when and how the selectivity of reagents with respect to substrates ought to vary with their reactivity. It incorporates a novel method of determining the effects of changing the nature of the reagent or the substrate on the nuclear structure of the reaction complex in its transition state. The model is shown to be capable of interpreting certain observed reactivity–selectivity behaviour which appears anomalous within the framework of orthodox theory. In particular departures from adherence to the Reactivity–Selectivity Principle and to Hammett-like correlation equations are interpreted.