The principle of imperfect synchronization: I. Ionization of carbon acids

The Principle of Imperfect Synchronization (PIS) states that a product stabilizing factor will lower the intrinsic rate of a reaction if it develops late, but increase the intrinsic rate if the factor develops early. It is shown in this paper that much of the structure-reactivity behavior of proton transfers involving carbon acids can be understood in the context of this principle. The factors discussed include the effect of resonance near the reaction site as well as in remote substituents, the polar effect of mote substituents, and the effects of solvation of reactants and products A sample matheatical formalism is developed to describe the contribution of each factor to the intrinsic rate constant. The possible reasons why there is a lack of synchronization between the various events which occur during the reaction are also discussed