Journal of the American Chemical Society

Entropy barriers to proton transfer

M Meot-Ner, SC Smith

Index: Meot-Ner, Michael; Smith, Sean C. Journal of the American Chemical Society, 1991 , vol. 113, # 3 p. 862 - 869

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Citation Number: 30

Abstract

Abstract: Proton transfer between sterically hindered pyridines and amines proceeds through locked-rotor, low-entropy intermediates. The reactions exhibit slow kinetics (efficiencies of 0. I-0.0001) and large negative temperature coefficients (up to k= CT*.'). The rates become slower and the temperature dependencies steeper with increasing steric hindrance. The observations are reproduced by a multiple complex-switching RRKM ...