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- W2952802934 abstract "The p-aminophenoxyl radical produced in the pulse radiolytic oxidation of p-aminophenol in aqueous solution has been examined by time-resolved resonance Raman methods. Eight Raman bands of fundamental vibrations were observed at microsecond times and at radical concentrations of -- 10/sup -5/M by excitation in the moderately strong absorption band of this radical at 444 nm (E = 6800 M/sup -1/ cm/sup -1/). This radical decays rapidly by second-order processes (2k = 2 x 10/sup 9/ M/sup -1/ s/sup -1/) so that at times longer than milliseconds the residual signals are very weak. The most intense Raman band of this radical, observed at 1636 cm/sup -1/, is ascribed to the Wilson 8a ring stretching mode and is similar in frequency to this mode in p-benzosemiquinone radical anion (1620 cm/sup -1/). The mixed CO/CN stretching frequency (1434 cm/sup -1/) is also very similar to that of the analogous mode in p-benzosemiquinone. This radical exhibits no strong Raman bands in the region of 1510-1520 cm/sup -1/ as do most other substituted phenoxyl radicals. Deuterium substitution of the NH/sub 2/ group shows that a band at 1673 cm/sup -1/ in the protonated radical is due to the symmetrical NH/sub 2/ bending vibration. Interestingly, thismore » deuterium substitution results in small increases in the frequencies of the CO/CN and ring stretching vibrations. The Raman data show very clearly, in agreement with conclusions from ESR data, that the structure of p-aminophenoxyl radical is more similar to that of a semiquinone than it is that of a phenoxyl radical. The high second-order rate constant observed for decay, however, indicates that the NH/sub 2/ group contributes significantly to modifying the redox properties of this radical.« less" @default.
- W2952802934 created "2019-06-27" @default.
- W2952802934 creator A5011667989 @default.
- W2952802934 creator A5064618353 @default.
- W2952802934 date "1984-07-31" @default.
- W2952802934 modified "2023-09-26" @default.
- W2952802934 title "ChemInform Abstract: RESONANCE RAMAN STUDIES OF PULSE RADIOLYTICALLY PRODUCED P-AMINOPHENOXYL RADICAL" @default.
- W2952802934 cites W2065472410 @default.
- W2952802934 doi "https://doi.org/10.1002/chin.198431045" @default.
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