Electrochemical studies of perfluoroalkyl and alkyl derivatives of cobalt(III) with quadridentate salicylaldimines at mercury and platinum electrodes

David J. Brockway, Bruce O. West, Alan M. Bond

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Abstract

The electrochemical reduction at mercury and platinum electrodes of a series of perfluoroalkyl (RF) and alkyl (RH) cobalt(III) NN′-ethylenebis(salicylaldimines) [CoR(salen)] has been studied in tetrahydrofuran by several techniques. Each class of compound is reduced similarly, [CoIIIR(salen)] e-→ [CoIIR(salen)]- e-→ [CoIR(salen)]2-, with the CoIIIRF complexes reducing most readily. Electron transfer and subsequent chemical reaction rates are different at the mercury and platinum electrodes implying that mercury-bridged intermediates may be formed at the mercury electrode. The [CoRF(salen)]- species are more stable than the alkyl complexes but do decompose to [Co(salen)] and perfluorocarbanions. The [CoRH(salen)]- anions rapidly yield [Co(salen)]- and the alkyl radical. Both complexes [CoR(salen)]2- decompose very rapidly to [Co(salen)]-.

Original languageEnglish
Pages (from-to)1891-1898
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number12
DOIs
Publication statusPublished - 1 Dec 1979

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