Relation between reactivity and electrochemical oxidation reduction potentials of organomercury compounds. I. Symmetrization of substituted ethyl α-bromomercuriophenylacetates

An approximate correlation equation relating the logarithms of the reaction rate constants for the symmetrization of para-substituted ethyl α-bromomercuriophenylacetates simultaneously with the electrochemical reduction and oxidation potentials of these compounds was obtained on the basis of molecular orbital perturbation theory and was confirmed by experimental data. This equation makes it possible to assess the degree of concertedness of the four-center reaction with respect to the terminal atoms of the reacting fragments of molecules and the role of nucleophilic assistance in the reaction. It is concluded that the organomercury compounds, which are oxidized relatively easily and are at the same time reduced relatively easily, must be readily symmetrized