The electrocarboxylation of chloroacetonitrile mediated by [Co(II)(phen)3]2+has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+have shown that [Co(I)(phen)3]+, an 18 electron complex, activates chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co-C bond cleavage. In carbon dioxide saturated solution, CO2insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen). © 2010 Elsevier B.V.
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