Arylaminyl radicals studied by laser flash photolysis of di-tert-butyl peroxide in the presence of arylamines

Laser flash photolysis of di-tert-butyl peroxide in the presence of arylamines (aniline, diphenylamine, carbazole, indole, 1-and 2-naphthylamine, and 1-pyrenylamine) is a clean, simple, and general method to generate and observe the corresponding arylaminyl radicals. Their absorption spectra are closely and systematically related to those of the π-isoelectronic arylmethyl radicals and triplet arylnitrenes. This relationship provides a useful guideline for the identification of transient intermediates and leads to a new proposal for the structure of the diphenylaminyl radical. The absolute rates of hydrogen abstraction from arylamines by the tert-butoxy radical depend on the resonance stabilization of the resulting arylaminyl radicals and approach the diffusion-controlled limit in highly conjugated systems. © 1987 American Chemical Society.

VIVO