Electrochemical reduction of 9,10-phenanthrenequinone, benzil and acenaphthenequinone in 1,1,1-trichloroethane (TCE)/TBAP under constant potential conditions provides an interesting entry to new coupling products through an electron-transfer reaction in solution to the chlorinated solvent. This electroinduced reaction points out the differences in the reaction pathway followed by these 1,2-dicarbonyl compounds depending on their geometry. The intermediates nature and their behavior, both in solution and at the electrode surface, are discussed. (C) 2015 Elsevier Ltd. All rights reserved.