Low-Temperature Electrochemistry III. Application to the Study of Radical Ion Decay Mechanisms

Richard P. Van Duyne*, Charles N. Reilley

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

69 Scopus citations

Abstract

The ability of low-temperature techniques to isolate the primary one-electron transfer oxidation or reduction process with a cryoquench of the coupled chemical reactions responsible for the radical ion decay mechanism is demonstrated. Successful cryoquenching, producing radical ion lifetimes of at least 2 sec, was achieved for: a radical anion fragmentation decay reaction (reduction of o- and p-iodonitrobenzene in dimethylformamide); a radical cation dimerization reaction (oxidation of triphenylamine in butyronitrile); a radical cation scavenging reaction by nucleophilic solvent impurity (oxidation of 1,2,3,6,7,8-hexahydropyrene in butyronitrile); and a radical cation scavenging reaction by nucleophilic solvent (oxidation of 9,10-diphenylanthracene in dimethylformamide). In contrast, the lifetime of the 9,10-dimethylanthracene cation radical in butyronitrile is less at low temperatures; the decay reaction involves a prior equilibrium reaction of the cation radical (DMA) with another cation radical (DMA) or with parent (DMA) and represents a case where new information has been provided by the low-temperature technique.

Original languageEnglish (US)
Pages (from-to)158-169
Number of pages12
JournalAnalytical Chemistry
Volume44
Issue number1
DOIs
StatePublished - Jan 1 1972

ASJC Scopus subject areas

  • Analytical Chemistry

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