RESUMO
Studies of the alpha-effect show increased reactivity of nucleophiles having lone pairs of electrons on atoms neighboring the lone pair involved in reactivity when compared to the basicity of the nucleophiles. Hammett-type plots and Brönsted-type plots of substituted methylphenyl sulfates vs hydrogen peroxide anions and substituted N-methylbenzohydroxanates (NMBH) with substituted methylarenesulfonates or substituted arenedimethylsulfonium ions have large rho or beta(nuc) values, indicating a putative tightening of the usual S(N)2 transition states (anti-Hammond effect). Electrochemical studies of S(N)2-SET or reactivity indicate that SET character occurs in looser transition states, whereas S(N)2 transition states are associated with greater tightness. The alpha-effects for the series of sulfonium salts in completion reactions for 3-ClNMBH anions and 3-nitrophenolate anions are (log k(alpha)/k(normal)) 1.124 for dimethylphenyl sulfonium, 1.512 for dimethyl-1-naphthyl sulfonium, 1.835 for dimethyl-9-anthracenyl sulfonium, and 1.137 for S-methyldibenzylthiophenium. Correlations of the sizes of alpha-effects with typical SET (or ET) experimental parameters and the inverse dependence of the size of the alpha-effect on electron demand indicate inclusion of SET character in these S(N)2 transition states, vs no (or at least diminished) SET character in normal transition states. This dichotomy of tighter S(N)2 transition states, but looser SET transition states indicated in the alpha-effect, is examined in the present work.
