Pulse-electrolysis stopped-flow

Nevertheless, these reactions still generate much controversy, as reactions between radical cations and nucleophiles should be forbidden unless electron transfer intervenes. Parker has suggested that the radical and cationic centers may be on different atoms [65]. Recent investigations on substituted DPA reactions show a strong substituent effect on the rate and, in some cases, the mechanism, as demonstrated in a recent pulse-electrolysis stopped-flow study [45]. 

A combination of the pulse electrolysis and the stopped-flow method has been used to study the reactivity of radical cations.A highly reactive transient radical cation can be generated very rapidly and its extremely fast reaction analyzed by the stopped-flow method. The... 

Greater time resolution can be gained by coupling pulse electrolysis to stopped-flow apparatus [44]. This technique has been used in the study of anthracene radical cation reactions with nucleophiles described later [45]. Electrochemical techniques are considered rather slow for studying these reactions the radical cations are much more conveniently generated and studied by laser flash photolysis. 

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