Electrocarboxylation of chloroacetonitrile mediated by a Ni(I) terpyridine complex: Voltammetric and spectroscopic studies - Archive ouverte HAL
Article Dans Une Revue Inorganica Chimica Acta Année : 2021

Electrocarboxylation of chloroacetonitrile mediated by a Ni(I) terpyridine complex: Voltammetric and spectroscopic studies

Résumé

Cyclic voltammetry and spectroelectrochemistry (e.p.r.) were used to investigate the mechanisms implied in the electrocarboxylation of chloroacetonitrile (Cl-CH2-CN, noted RCl) mediated by [Ni(II)(terpy)2]2+. The oxidative addition of chloroacetonitrile on the electrogenerated [Ni(I)(terpy)]+ yields an alkyl-nickel R-Ni(III) complex which is reduced into an alkyl-nickel(II). E.p.r study shows that the homolytic nickel-carbon bond cleavage seems to be the more probable pathway to form the organic radical R-which is reduced to R−. Under carbon dioxide atmosphere, cyclic voltammetry studies show that CO2 was added on the alkyl-Ni(III) complex giving probably a CO2 adduct which is reduced to RCO2-Ni(II) complex allowing to release the carboxylate RCO2− and the active [Ni(I)(terpy)]+ complex. Controlled potential electrolyses showed that good carboxylated and faradic yields were obtained.
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hal-03270705 , version 1 (24-05-2023)

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Dancheng Chen, Paul-Louis Fabre, Olivier Reynes, Nadia Chouini-Lalanne, Valérie Sartor. Electrocarboxylation of chloroacetonitrile mediated by a Ni(I) terpyridine complex: Voltammetric and spectroscopic studies. Inorganica Chimica Acta, 2021, 524, pp.120442. ⟨10.1016/j.ica.2021.120442⟩. ⟨hal-03270705⟩
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