Comparison between Experimental and Theoretical Scales of Electrophilicity in Benzhydryl Cations

The theoretical electrophilicity pattern of a series of benzhydryl cations as described in terms of a model based on global reactivity indexes is compared with an experimental scale recently proposed by Mayr et al. J. Am. Chem. Soc. 2001, 123, 9500. A good correlation between both theoretical and experimental quantities is found. The effect of chemical substitution on the electrophilic power of these charged electrophiles may also be assessed as local responses at the active site, in terms of a global contribution described by changes in global electrophilicity with reference to the dianisylcarbenium ion, and a local contribution described by the variations in electrophilic Fukui function at that site.