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

✍ Scribed by Torben Lund; Henning Lund

• Publisher: Elsevier Science
• Year: 1986
• Tongue: French
• Weight: 293 KB
• Volume: 27
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)83950-7

✦ Synopsis

The rate of the reaction between the anion of 1,4-dihydro-4-methoxycarbonyl-l-methylpyridine (1-j and sterically hindered alkyl halides,and between the perylene dianion (Pe'-) and t-butyl chloride and see-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') with the same standard potential as Y/l-, resp. Pe;/Pe'to the corresponding alkyl hali- des. The kinetic results strongly suggest that a SET mechanism is the rate-determining step in these nucleophilic substitutions.