Oxidation processes for tetraethyllead and tetramethyllead in dichloromethane at mercury electrodes

A. M. Bond, N. M. McLachlan

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Abstract

Electrochemical studies on tetraethyllead and tetramethyllead at mercury electrodes in dichloromethane are characterised by a one electron oxidation process in contrast to the two electron step reported for the tetraphenyllead compound. Short time pulse techniques and coulometric techniques with tetraethyllead are consistent with the mechanism: {A figure is presented}{A figure is presented}. The initial reaction pathway with the methyl analogue is the same. However, long time scale experiments with tetramethyllead are modified by further reactions of the kind {A figure is presented}. New studies on tetraphenyllead employing variable time domain pseudo derivative normal pulse polarography show that the oxidation of this compound is also consistent with a one electron process at very short times. However the Φ3Pb{radical dot} radical is slower to dimerise than the alkyllead radicals and so direct reaction with ΦHg+ is observed to generate Φ3Pb+ and Φ2Hg. A subsequent electrochemical process involving Φ3Pb+ at the mercury electrode is responsible for the overall two electron transfer reaction observed.

Original languageEnglish
Pages (from-to)37-48
Number of pages12
JournalJournal of Electroanalytical Chemistry
Volume194
Issue number1
DOIs
Publication statusPublished - 10 Oct 1985

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