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The electron spin resonance (esr) spectra of eighteen para-substituted cumyl radicals were analyzed. The relationship between the β-hyperfine coupling (β-hfc) constants of these cumyl radicals and the corresponding α-hfc constants of benzyl radicals was studied. Although there is a general trend for the α- and β-hfc values to vary in a similar manner, specific deviations from a linear correlation between these parameters were observed. These deviations were rationalized by considering charge effects on spin delcoalization. The correlation coefficient for the linear regression analysis of these α- and β-hfc values was found to significantly improve when β arameters reflecting charge effects on spin delocalization were included in an extended Hammett treatment of the spectral data.

canadian journal of chemistry

Substituent effects on benzyl radical hyperfine coupling (hfc) constants. Part 3. Comparison of the α-hfc for substituted benzyl radicals with the β-hfc for substituted cumyl radicals