Abstract
The reaction profile of the 1,3-prototropic rearrangement of propene involving the hydroxide ion was studied by the RHF/6-31+G*, MP2/6-31+G*, and B3LYP/6-31+G* ab initio methods within the framework of the gas-phase and Born–Onsager models (the latter including solvent effects). Propene isomerization in the presence of the hydroxide ion in the gas phase may occur with participation of a base proton with the intermediate formation of a water complex of the allyl ion. The transition state energy of this transformation is lower than the total energy of the starting hydroxide ion and propene and much lower than the sum of the energies of the isolated propenide ion and water molecule. An activation barrier arises when the solvent effect is included in calculation within the framework of the Born–Onsager model; the intermediate complex is much less stable than the complex considered in the gas-phase model. As in the latter, the mechanism of multiple bond migration is energetically preferable to the mechanism involving proton transfer to the reaction medium.
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Kobychev, V.B., Pavlova, N.V. Double Bond Migration Mechanism in Allyl Systems Involving the Hydroxide Ion. 1. Gas-Phase and Born–Onsager Models. Journal of Structural Chemistry 45, 12–19 (2004). https://doi.org/10.1023/B:JORY.0000041496.30502.85
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DOI: https://doi.org/10.1023/B:JORY.0000041496.30502.85