Abstract:Radical cations were generated from different phenyl-substituted aziridines by pulse radiolysis in aqueous solution containing TlOH In the pulse radiolysis experiments in aqueous solution, the primary oxidants can also be observed,whereas in n-butyl chloride a transient at 325 nm remains unidentified. In the Laser Flash experiments, both types of radical cations were also observed.
The radical cations of cyclopentane- and urazole-annelated
azoalkanes and housanes were generated by
pulse radiolysis and the transients characterized spectrally and
kinetically by time-resolved optical monitoring. For
the bridgehead-substituted diphenyl derivatives of the
cyclopentane-annelated azoalkane 1 and housane 2
only the
corresponding proximate 1,2 radical cation species were observed,
generated from the initially formed and too short-lived (<1 μs) distonic 1,3 radical cation by 1,2-methyl migration.
In contrast, for the corresponding urazole-annelated
azoalkanes 4, the initial distonic 1,3 radical cations
5
•+ were detected, and of these
the methyl-substituted
5b
•+
deprotonates to the radical
5b
•.
The radical cations of 1-butyl-trans-2,3-diphenyl aziridine (1), 1-butyl-2-phenyl aziridine (2), 1,2-diphenyl aziridine (3) and 1-(p-methoxyphenyl)-2-phenyl aziridine (4) were generated upon laser flash photolysis in aqueous and aqueous acetonitrile solutions by direct photoionisation as indicated by the broad absorption band of the solvated electron above 550 nm as well.
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