Abstract
Ab initio calculations of the thermodynamic stability order of six acyclic unsaturated hydrocarbons are presented. The results are in reasonable agreement with the experimentally observed order in the equilibrium mixture of isomers resulting from the base-catalyzed isomerizations. The charge distribution and molecular electrostatic potential of two postulated intermediate carbanions involved in these isomerizations are also calculated in order to explain their initial product ratios which have been observed to differ from the thermodynamical order. These properties fail to reproduce the observed kinetic behaviour. Inclusion of polarization does not improve essentially these results. An estimate of the activation entropy on the basis of the shape of the potentials permits of an interpretation in agreement with the observed reactivity.
Published Version
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