Theoretical Prediction of Activation Free Energies of Various Hydride Self-Exchange Reactions in Acetonitrile at 298 K

[Image: see text] Hydride transfer reactions are very important chemical reactions in organic chemistry. It has been a chemist’s dream to predict the rate constants of hydride transfer reactions by only using the physical parameters of the reactants. To realize this dream, we have developed a kinetic equation (Zhu equation) in our previous papers to predict the activation free energies of various chemical reactions using the activation free energies of the corresponding self-exchange reactions and the related bond dissociation energies or redox potentials of the reactants. Because the activation free energy of the hydride self-exchange reaction is difficult to measure using the experimental method, in this study, the activation free energies of 159 hydride self-exchange reactions in acetonitrile at 298 K were systematically computed using an accurately benchmarked density functional theory method with a precision of 1.1 kcal mol(–1). The results show that the range of the activation free energies of the 159 hydride self-exchange reactions is from 16.1 to 46.6 kcal mol(–1). The activation free energies of 25 122 hydride transfer reactions in acetonitrile at 298 K can be estimated using the activation free energies of the 159 hydride self-exchange reactions and the corresponding heterolytic bond dissociation free energies of the reactants. The effects of the heteroatom, substituent, and aromaticity on the activation free energies of hydride self-exchange reactions were examined. The results show that heteroatoms, substituents at the reaction center, and the aromaticity of reactants, all have remarkable effects on the activation free energy of hydride self-exchange reactions. All kinetic information provided in this work on the hydride self-exchange reactions in acetonitrile at 298 K should be very useful in chemical labs and chemical industry.