Iminoxyl radicals and stable products from the one-electron oxidation of 1-methylindole-3-carbaldehydeoximes
Abstract
The radical intermediates and the stable products formed on one-electron C
NOH to yield the radical
C
NOH]˙+, which exist in prototropic equilibria with the neutral iminoxyl radicals [
C
NO]˙ (pKa
= 3.53 ± 0.03 and 5.01 ± 0.01 at ionic strength 0.05 M, respectively). This was confirmed by the observed primary salt-effect which accelerated the decay of the radical
C
NOCH3]˙+. At low concentrations of 2a and high dose rates the 2a radicals [
C
NO]˙ decayed bimolecularly via unstable dimers to the
C
O, with higher concentrations and lower dose rates favouring the chain-catalysed isomerisation of the N-hydroxyimino moiety. Radicals from 4a decay bimolecularly to form unstable dimers which degrade to produce an