Correlation analysis in the chemistry of free radicals

• Published data available by now on the use of correlation analysis in the free-radical chemistry are discussed systematically. The scales of <> sigma -constants of substituents proposed previously are analysed. It is shown that none of them is suitable as a general scale because almost in all cases, it is impossible to separate correctly the proper radical and polar contributions to the overall effect of substituents. A new approach to the quantitative estimation of the relationship between the structure and reactivity of molecules in free-radical processes is proposed and called r(-2)-analysis.

Keyword

bond-dissociation energies

hyperfine coupling-constants

carbon-centered radicals

benzyl-type radicals

inductive electronegativity scale

electron reduction potentials

substituted methyl radicals

cis-trans isomerization

tert-butoxy radicals

delta-d scale

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