Browsing by Author "Critchlow, J. E."

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    Prediction of Transition State Configuration in Concerted Reactions from the Energy Requirements of the Separate Processes
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (9), 1972) Critchlow, J. E.
    A simple method is presented for calculating the configuration and energy of the transition state in a concerted reaction from the energies required to form the intermediates of the hypothetical step-wise processes. The model is tested by comparison of predicted and observed structure-reactivity relations. Substitution in the attacking or leaving portion of a concerted reaction system should give rise to changes exclusively in the more remote bond and hence to a linear free energy relationship, while non-linear correlations are possible when substitution occurs in the central moiety. Taken n conjunction with experimental evidence, the model suggests that in carbonyl hydration reactions nucleophilic attack occurs synchronously with a single proton transfer. The conditions favouring bifunctional catalysis are discussed.