| Autor: |
Nadia Chouini-Lalanne, Paul-Louis Fabre, Valérie Sartor, Olivier Reynes, Dancheng Chen |
| Rok vydání: |
2013 |
| Předmět: |
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| Zdroj: |
Journal of Electroanalytical Chemistry. 711:25-31 |
| ISSN: |
1572-6657 |
| Popis: |
Mechanisms implied in the electrocarboxylation of chloroacetonitrile (Cl–CH 2 –CN, noted RCl) mediated by [Co(II)(phen) 3 ] 2+ have been investigated by cyclic voltammetry and spectroelectrochemistry (UV–Visible and e.p.r.). The studies showed that the oxidative addition of chloroacetonitrile on the electrogenerated [Co(I)(phen) 2 ] + yields an alkyl-cobalt R-Co(III) complex. This complex can either be reduced into an alkyl-cobalt(II) or undergoes a homolytic cobalt–carbon bond cleavage to form the organic radical R and the [Co(II)(phen) 2 ] 2+ complex. Whatever the process, R − and [Co(I)(phen) 2 ] + were produced. In presence of free phenanthroline, the catalytic behaviour of the complex was strongly vanished because the formation of the active complex [Co(I)(phen) 2 ] + is restricted. Under CO 2 atmosphere, the catalytic electrocarboxylation of chloroacetonitrile was observed. Bulk electrolyses showed that the carboxylated and faradic yields depended on the applied electrolysis potential and free phenanthroline concentration. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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