Electrohydrodimerization Reactions: IV . A Study of the Effect of Alkali Metal Ions on the Hydrodimerization of Several 1,2‐Diactivated Olefins in DMF Solutions by Chronoamperometry and Chronocoulometry

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Abstract
The reduction of the activated olefins: dialkyl fumarates (alkyl = methyl, ethyl, butyl), ethyl cinnamate and cinnamonitrile in tetra‐n‐butylammonium iodide‐dimethylformamide solutions in the absence and presence of Li+, Na+, and K+ was studied by double potential step chronocoulometric and chronoamperometric techniques, cyclic voltammetry, and controlled potential coulometry. The results in the absence of alkali metal ions confirmed the previous mechanism involving formation of the radical anion, , followed by dimerization; no evidence of appreciable adsorption of the parent olefin or was found. The addition of alkali metal ion (M+) greatly increased the rate of the dimerization reaction and a mechanism based on formation of the ion pair, , followed by reaction of with or coupling of two species is proposed based on an analysis of the kinetic data. The addition of Li+ also decreased the extent of polymer formation during bulk electrolysis experiments.

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