Abstract
A single electron transfer (SET) photosensitization technique in conjunction with time-resolved, laser spectroscopy has been employed to generate and kinetically analyze decay processes of anilinium radicals derived by one-electron oxidation of α-anilinocarboxylates, β-anilinoalcohols, and α-anilinosilanes. In this manner, the rates of unimolecular decarboxylation of aniliniumcarboxylate radicals were determined to be in the range 106−107 s-1 and dependent upon solvent polarity, the nature of the metal cation, and substituents on the aniline ring, nitrogen, and α-carbon. In addition, kinetic analysis of base-induced retro-aldol fragmentations of cation radicals arising by SET oxidation of β-anilinoalcohols has shown that they occur with bimolecular rate constants which vary from 104 to 105 M-1 s1. These values are close to those for α-deprotonation reactions of related N,N-dialkylanilinium radicals. The retro-aldol fragmentation rates, like those for α-decarboxylation, also vary in a patterned way with ch...
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