Electronegativity, nucleophilicity effects

Hence, nucleophilic reactions of the superoxide ion are typical. This ion can be compared with the thiophenoxide and thiocyanate ions with respect to nucleophilicity. The cause of such high nucleophilicity lies in a so-called a-effect In 0—0 ion, an attacking site (O ) adjoins directly to a site (O ) with a significant electronegativity. This effect usually confers special activity to nucleophiles. The effect can be additionally enhanced by including the 0—0 group in sulfenate. 

Because the addition steps are generally fast and consequently exothermic chain steps, their transition states should occur early on the reaction coordinate and therefore resemble the starting alkene. This was recently confirmed by ab initio calculations for the attack at ethylene by methyl radicals and fluorene atoms. The relative stability of the adduct radicals therefore should have little influence on reacti-vity 2 ). The analysis of reactivity and regioselectivity for radical addition reactions, however, is even more complex, because polar effects seem to have an important influence. It has been known for some time that electronegative radicals X-prefer to react with ordinary alkenes while nucleophilic alkyl or acyl radicals rather attack electron deficient olefins e.g., cyano or carbonyl substituted olefins The best known example for this behavior is copolymerization This view was supported by different MO-calculation procedures and in particular by the successful FMO-treatment of the regioselectivity and relative reactivity of additions of radicals to a series of alkenes An excellent review of most of the more recent experimental data and their interpretation was published recently by Tedder and... 

A free radical is stabilized by an X substituent (Figure 13a) through a two-orbital, three-electron 7r-type interaction. The nucleophilicity of the radical is greatly increased. The X -substituted free radicals are more easily oxidized. The n effects of X substitution are somewhat augmented by the inductive effect of the electronegative X in stabilizing the radical. 

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