Chen, Dancheng and Fabre, Paul-Louis
and Reynes, Olivier
Electrocarboxylation of chloroacetonitrile by a Cobalt(I) complex of terpyridine.
(2011)
Electrochimica Acta, 56 (24). 8603-8610. ISSN 0013-4686
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(Document in English)
PDF (Author's version) - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader 420kB |
Official URL: http://dx.doi.org/10.1016/J.ELECTACTA.2011.07.052
Abstract
The electrocarboxylation of chloroacetonitrile (NC–CH2–ClRCl) mediated by [CoIIL2]2+ (L = terpyridine) was investigated by cyclic voltammetry. Electrochemical studies under argon atmosphere showed that the monoelectronic reduction of [CoIIL2]2+ yielded a Cobalt(I) complex which after the loss of a terpyridine ligand reacted with chloroacetonitrile. The oxidative addition of chloroacetonitrile on [CoIL]+ gave an alkylCobalt(III) complex [R–CoIIIL]2+ which was reduced into an alkylCobalt(II) complex, highly unstable and decomposed into an alkyl anion and a Cobalt(II) complex. Under carbon dioxide atmosphere, Cobalt(I) complex was shown to be unreactive towards CO2 but CO2 insertion was observed in the alkylCobalt(III) complex [R–CoIIIL] 2+ giving probably a CO2 adduct [R–CoIIIL(CO2)]2+. This adduct presented a strong adsorption at the carbon electrode and was reduced at potential less cathodic than the one of alkylCobalt(III) complex. After reduction, the carboxylate RCO2− (NC–CH2–CO2−) was released and a catalytic bielectronic carboxylation of chloroacetonitrile took place. Controlled potential electrolyses confirmed the catalytic process and gave for cyanoacetic acid faradic yields up to 60% under low overpotential conditions.
Item Type: | Article |
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Additional Information: | Thanks to Elsevier editor. The definitive version is available at http://www.sciencedirect.com The original PDF of the article can be found at : http://www.sciencedirect.com/science/article/pii/S0013468611010875 |
HAL Id: | hal-03539214 |
Audience (journal): | International peer-reviewed journal |
Uncontrolled Keywords: | |
Institution: | French research institutions > Centre National de la Recherche Scientifique - CNRS (FRANCE) Université de Toulouse > Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE) Université de Toulouse > Université Toulouse III - Paul Sabatier - UT3 (FRANCE) |
Laboratory name: | Laboratoire de Génie Chimique - LGC (Toulouse, France) - Procédés électrochimiques (PE) |
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Deposited On: | 04 Jul 2012 12:37 |
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