Comprehensive Study of the Methyl Effect on the Solvolysis Rates of Bridgehead Derivatives

The effect of a bridgehead methyl group on the hydride ion affinity in the gas phase of bicyclo[1.1.1]pent-1-yl (1(+)), 1-norbornyl (3(+)), cubyl (5(+)), 1-adamantyl (7(+)), bicyclo[2.2.2]oct-1-yl (9(+)),
and bicyclo[3.1.1]hept-1-yl (11(+)) cations has been studied using density functional theory and ab initio
methods. It is concluded that the methyl group always increases the stability of the substituted cations.
The effect of the solvent on the stability of methyl-substituted cations in relation to the unsubstituted cations
has been studied using the polarizable continuum model of the self-consistent reaction field theory. In the
case of rearranging cations, the nucleophilic assistance of the solvent is determined by means of the
interaction energy of the corresponding water complexes. It is concluded that the solvent causes the relative
stabilization of the parent cations. As a consequence, most of the methyl-substituted bridgehead derivatives
show a lower solvolysis rate than the corresponding unsubstituted compounds. A nonqualitative explanation
of the methyl effect on the relative stability of bridgehead cations in both gas phase and solution is given
for the first time. The ratios of solvolysis products in the case of rearranging bridgehead cations have also
been computed from the relative stability of the intermediate water complexes.