The radical anion of 1,4-naphthoquinone has been prepared by electrochemical reduction in dimethylformamide and by alkali-metal reduction in 1,2-dimethoxyethane. The e.s.r. spectrum of the radical anion in dimethylformamide can be readily interpreted in terms of three pairs of equivalent protons. However, in 1 ,Zdimethoxyethane, association of the alkali-metal counter-ion with one of the carbonyl groups removes the equivalence within each of these pairs. Linewidth alternation is observed in the e.s.r. spectrum when either Na+, K+ or Cs+ is the counter-ion as a result of intramolecular cation migration between equivalent sites adjacent to the two carbonyl groups. The rate of migration varies in the sequence Cs+ > K+ > Na+ > Li+, indicating that Li+ interacts more strongly with the radical anion than (say) Cs+. The disruption of the spin distribution within the radical anion, which is also greatest when Li+ is the counter-ion, supports this conclusion. ~~ ~ T/K 42-H) 43-H) 45-H) 46-H) 47-H) 48-H) ~/ 1 0 -~ s
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