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)]-.
|Number of pages||8|
|Journal||Journal of the Chemical Society, Dalton Transactions|
|Publication status||Published - 1 Dec 1979|