The Mills-Nixon effect and chemical reactivity - methyl cation affinity ofsome cycloalkabenzenes

The problem of the methyl cation attack on carbon atoms belonging to the be nzene moiety fused to small rings is explored by the ab initio models at th e MP2 level of sophistication. It is shown that the beta -position is more reactive than the alpha -site in kinetically controlled reactions, which is in accordance with the original Mills-Nixon postulate. On the other hand, it appears that in thermodynamically controlled electrophilic substitution reactions the alpha -site should be slightly preferred for three-, four- an d five-membered annelated rings. The differences between the methyl cation affinities MCA(beta) and MCA(alpha) are analyzed and resolved into angular strain and the cationic resonance contribution. The latter involves the hyp erconjugation/conjugation and relaxation effects. It turns out that the ang ular strain contribution is inversely proportional to the size of the annel ated ring, whereas the opposite is the case for thecationic resonance inter action. Their interplay determines the selectivity and its extent in the el ectrophilic substitution reactions. The same analysis is applicable to othe r electrophilic groups.