Abstract
Alkyl radical formation in halocarbon matrices containing the parent radical cation has been studied for various alkyl-substituted cyclohexanes. Contrary to the reaction mechanism suggested earlier, no direct relationship was found between the locations of high hydrogen spin density in the cation and the site of the π-type alkyl radicals which are formed. Among the cis and trans isomers of di- and tri-methylcyclohexanes, tertiary alkyl radicals were found to be always formed most preferentially whenever the corresponding solute molecule has at least one axial methyl group on the chair conformation. The other isomers gave secondary alkyl radicals with the site in the ring structure.
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