Single electron-transfer as rate-determining step in an aliphatic nucleophilic substitution

Torben Lund*, Henning Lund

*Corresponding author for this work

Research output: Contribution to journalJournal articlepeer-review


The rate of the reaction between the anion of 1,4-dihydro-4-methoxycarbonyl-1-methylpyridine (1- and sterically hindered alkyl halides, and between the perylene dianion (Pe2-) and t-butyl chloride and sec-butyl bromide has been measured by electrochemical techniques. The rate was found to be close to the rate of single electron-transfer (SET) from anion radicals (A{minus sign, dot below}) with the same standard potential as 1/1-, resp. Pe{minus sign, dot below}/Pe2- to the corresponding alkyl halides. The kinetic results strongly suggest that a SET mechanism is the rate-determining step in these nucleophilic substitutions.

Original languageEnglish
JournalTetrahedron Letters
Issue number1
Pages (from-to)95-98
Number of pages4
Publication statusPublished - 1986
Externally publishedYes

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