Relationship between local electrophilicity and rate coefficients for the hydrolysis of carbenium ions

The local electrophilicity of a series of 28 carbenium ions has been ranked within a theoretical absolute scale. New substituent constants are introduced to account for the responses of the electrophilicity pattern induced by multiple substitutions at the carbocation site. The model is used to predict rate coefficients ordering in terms of the experimental hierarchy of electrophilicity established for these systems [Minegishi, S.; Mayr, H. J. Am. Chem. Soc. 2003, 125, 286].