GROUP ELECTRONEGATIVITY AND FUKUI FUNCTION STUDIES OF THE SUBSTITUENT EFFECTS IN AROMATIC AND INORGANIC SYSTEMS

The group electronegativities (GE) of molecular fragments, including the environmental contributions due to both the electrostatic interactions and electron distribution relaxation, and the Fukui function (FF) indices of the charge sensitivity analysis (CSA) are correlated with the known substituent effects in molecular systems. The semiempirical CSA in the atoms-in-molecules (AIM) resolution has been applied to substituted benzenes and square platinum complexes treated as illustrative examples. The calculated FF indices and GE are both shown to constitute adequate reactivity criteria that qualitatively reproduce the known substituent effects. The FF index (second-order property) is found to be a more sensitive detector of the substituent influence than is the corresponding GE parameter (first-order property).