Electrochemical reduction of 1,2-dibromohexane (1) and 1,6-dibromohexane (2) at silver cathodes in dimethylformamide (DMF) containing tetramethylammonium perchlorate (TMAP) has been investigated with the aid of cyclic voltammetry and controlled-potential electrolysis. Cyclic voltammograms for reduction of 1 and 2 both exhibit a single irreversible cathodic peak associated with reduction of carbonbromine bonds; however, the cathodic peak potential (-0.33 V) for 1 is significantly less negative than that (-1.00 V) for 2, and the peak current for 1 is approximately half of that for 2. Cyclic voltammograms for 0.5-20.0 mM solutions of 1 and 2, separately, show that the parameter I-pc/C* increases as the concentration (C*) decreases; this trend is likely due to a combination of adsorption phenomena and a potential-dependent transfer coefficient (alpha). Coulometric n values and product distributions arising from bulk electrolyses of 5.0 mM solutions of 1 and 2 depend on the positions of the bromine atoms: (a) for 1, n was 2.13 and 1-hexene was the only product; (b) for 2, n was 2.12 and a mixture of products was obtained [1-hexene (21%), n-hexane (37%), 1,5-hexadiene (22%), 5-hexen-1-ol (9%), and a trace of n-dodecane]. When 2 was electrolyzed in the presence of a proton or deuteron donor (2,2,2-trifluoroethanol or D2O), the n value and the amount of n-hexane increased, whereas 1-hexene and 1,5-hexadiene decreased in yield. We conclude that reduction of 1 follows a concerted mechanism, but that reduction of 2 proceeds via carbanionic intermediates. (C) 2015 Elsevier Ltd. All rights reserved.