A dinickel Schiff base complex (Ni-2(II)L) containing two salen units has been synthesized and characterized by NMR and mass spectrometry. The complex was used for the catalytic reduction of 1- and 2-bromooctanes and its electrochemical behavior, which is similar to that of nickel salen, was studied by cyclic voltammetry and controlled-potential electrolysis. Due to the proximity of the two nickel centers, the yield of octyl dimers is slightly higher for the electrochemical reduction of 2-bromooctane catalyzed by the dinickel complex than that by nickel salen. However, the yield of hexadecane does not increase for the catalytic reduction of 1-bromooctane, which can give more reactive primary radicals. In addition to the formation of various products, octylation of the dinickel complex takes place to a further extent for the reduction of 2-bromooctane than 1-bromooctane. Compared with nickel salen-catalyzed reduction, the electrochemical data also indicate that more octyl groups may incorporate into the dinickel complex. Mechanistically, the catalytic reduction of the bromooctanes involves the intermediacy of primary or secondary octyl radicals. (C) 2008 Elsevier BY. All rights reserved.