Single Electron Transfer as Rate-Determining Step in an Aliphatic Nucleophilic Substitution.

Dependence of nonadiabatic intramolecular dissociative electron transfers on stereochemistry and driving force

“…Fig. 5 shows the activation-driving force relationship obtained with the 2 series in comparison with that previously obtained with the corresponding cis isomers 1 and the corresponding second-order fit (dashed line) to available ET rate constant values pertaining to the homogeneous dissociative reduction of tertiary bromides [25,47]. As shown by the error bars in Fig.…”

A Century of Organic Electrochemistry

“…For sterically hindered alkyl halides the two rates were practically the same, indicating that in this aliphatic nucleophilic substitution the rate of the transfer of a single electron from the nucleophile to the alkyl halide was the rate-determining step. 180,181 In less sterically hindered alkyl halides the rate of substitution was faster than the expected rate of electron transfer indicating either a competition between electron transfer and S N 2 or a kind of hybrid between the two mechanisms. An attractive way to obtain stereoselective reactions would be to use enzymatic reactions in which the active form of the enzyme was regenerated electrochemically.…”

Oxidation and Reduction of Halogen‐containing Compounds

“…Simonet and coworkers [135] pointed out that a catalytically formed alkyl radical can react with an aromatic anion radical to form an alkylated aromatic hydrocarbon. Additional, comparatively recent work has centered on electron transfer between aromatic anion radicals and 1,2-dichloro-1,2-diphenylethane [136], on reductive coupling of tert-butyl bromide with azobenzene, quinoxaline, and anthracene [137], and on the reactions of aromatic anion radicals with substituted benzyl chlorides [138], with vinyl bromides, 2-bromoindene, and 7,7-dichlorobicyclo[4.1.0]heptane [139], and with bornyl, isobornyl, and exo-and endonorbornyl bromides [140].…”