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Keywords:

  • carbocations;
  • hydride transfer;
  • kinetics;
  • linear free energy relationships;
  • reactivity parameters

Abstract

Rates of hydride transfer from several hydride donors to benzhydrylium ions have been measured at 20 °C and used for the determination of empirical nucleophilicity parameters N and sN according to the linear free energy relationship log k20 °C=sN(N+E). Comparison of the rate constants of hydride abstraction by tritylium ions with those calculated from the reactivity parameters sN, N, and E showed fair agreement. Therefore, it was possible to convert the large number of literature data on hydride abstraction by tritylium ions into N and sN parameters for the corresponding hydride donors, and construct a reactivity scale for hydride donors covering more than 20 orders of magnitude.