Study of PhotoinducedN-Hydroxy-arylnitroxide Radicals (ArNO•OH) by Time-Resolved EPR

Abstract

The photoreduction of aromatic nitro compounds by alcohols is a well-known reaction; however, the first stages of its mechanism remain controversial. This study aims at characterizing the "primary" radicalar transients involved in this reaction by EPR spectroscopy. Laser flash photolysis (lambda = 266 nm) of nitrobenzene, 5-nitrouracil, p-nitroacetophenone, o-propylnitrobenzene, and 2-nitroresorcinol in ethylene glycol was followed by time-resolved EPR spectroscopy. In all reported TR-EPR spectra, except those obtained from the photolysis of 2-nitroresorcinol, the key intermediate N-hydroxy-arylnitroxide radicals (ArNO*OH, 1-4) could be identified unambiguously. In 2-nitroresorcinol, the radical anion (ArNO*O(-), 5) and a sigma iminoxy radical (6) were observed, and a third radical (7) remains unidentified. These observations indicate that two radicalar mechanisms (by H* transfer and by electron transfer) are competing in the photoreduction mechanism. The attribution of the EPR spectra was helped by DFT calculations of the hyperfine coupling constants (hcc's).