Stereochemical effects in organic electrochemical kinetics

Summary A d.c. and a.c. polarographic study of the cyclooctatetraene system in dimethyl-formamide-tetrabutylammonium perchlorate is presented. Rate parameters are obtained for the reduction at mercury of cyclooctatetraene, the cyclooctatetraene anion radical and 1,3,5-cyclooctatriene, as well as for the homogeneous protonation of the cyclooctatetraene dianion. The results quantitatively confirm previous evidence suggesting a dramatic rate difference associated with the first and second reduction step of cyclooctatetraene. The origin of this phenomenon is discussed.

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