Cyclic 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 employed to investigate the direct reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) at a carbon cathode in dimethylformamide (DMF) containing 0.10 M tetra-n-butylammonium tetrafluoroborate (TBABF(4)) as well as the nickel(1) salen-mediated reduction of CFC-113 in the same medium. Cyclic voltammograms for direct reduction of CFC-113 show two irreversible cathodic peaks attributable to formation of, first, 1-chloro-1,2,2-trifluoroethene (CFC-1113) and, second. trifluoroethene (HFC-1123); bulk electrolyses of CFC-113 at potentials corresponding to each of the cathodic peaks afford CFC-1113 and HFC-1123, respectively, in essentially quantitative yield. Cyclic voltammograms for reduction of nickel(11) salen in the presence of CFC-113 provide evidence for the catalytic formation of CFC-1113 and HFC-1123, and bulk electrolyses involving electro-generated nickel( I) salen lead to mixtures of CFC-1113 and HFC-1123, although 1,1,1,2-tetrafluoroethane (HFC-134a) has been detected as a minor product. It has been determined with the aid of HPLC-ESI-MS that the salen ligand of the nickel(1) catalyst is modified during the catalytic reduction of CFC-113. A mechanistic scheme is proposed for the direct reduction of CFC-113. (C) 2012 Elsevier B.V. All rights reserved.