Parametric variation and chemical effects: SCF treatment of arylmethyl cations

Abstract

The solvolytic reactivity of arylmethyl tosylates can be well correlated by simple full-overlap treatments of the SCF Mulliken type. These types of theories balance more adequately the energetic contribution due to effects which can be classified as ‘charge–dipole’ and ‘delocalization’ derived, than the corresponding zero-differential overlap theory, CNDO/2. The sensitivity of the predictions to the parameters used in the theories gives indications of the nature of the qualitative interactions present in the arylmethyl systems.