Nickel(I) salen-catalyzed reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113): CO2-mediated carbon–fluorine bond cleavage

Publication date: Available online 24 February 2020Source: Journal of Electroanalytical ChemistryAuthor(s): J. Tyler Barnes, Rachyl A. Adams, Seyyedamirhossein Hosseini, Elizabeth R. Wagoner, Dennis G. PetersAbstractCyclic voltammetry, controlled-potential (bulk) electrolysis, gas chromatography (GC), gas chromatography–mass spectrometry (GC–MS), and high-performance liquid chromatography–electrospray ionization–mass spectrometry (HPLC–ESI–MS) have been used to investigate the direct and nickel(I) salen-catalyzed reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in both Ar- and CO2-saturated dimethylformamide (DMF) containing 0.10 M tetra-n-butylammonium tetrafluoroborate (TBABF4). Cyclic voltammograms show one irreversible cathodic peak for direct reduction of CFC-113 in CO2-saturated DMF to afford 1-chloro-1,2,2-trifluoroethene (CFC-1113), whereas cyclic voltammograms in Ar-saturated DMF exhibit two irreversible cathodic peaks. Bulk electrolyses of CFC-113 in CO2-saturated DMF at a potential 400 mV more negative than the resolved cathodic peak cause partial reduction of CFC-1113 to yield di-, tri-, and tetrafluoro species. Cyclic voltammograms for reduction of nickel(II) salen in the presence of CFC-113 in CO2-saturated DMF show two cathodic peaks attributable to formation of CFC-1113 and HFC-1123; cyclic voltammograms in Ar-saturated DMF exhibit similar behavior. Bulk electrolyses involving electrogenerated nickel(I) salen in CO2-saturated DMF yi...

Source: Journal of Electroanalytical Chemistry - February 24, 2020 Category: Chemistry Source Type: research