Reductive coupling of benzyl bromide catalyzed by a novel dicobalt complexhaving two salen units

A novel dicobalt complex [(Co2L)-L-II] has been synthesized, where (L)(4-) is a dinucleating ligand derived by the 2 : 2 : 1 condensation of ethylened iamine, salicylaldehyde, and 5,5'-methylenebis(salicylaldehyde), and it has two N2O2 metal-binding sites which are linked to each other with a methyle ne spacer. This complex was characterized by UV-VIS, IR, and NMR as well as mass spectroscopy. Its redox behavior was investigated in dmf using cyclic voltammetry in comparison with that for the corresponding mononuclear comp lex [Co(salen)]. The redox couples to Co-III-Co-II and Co-II-Co-I for [(Co2 L)-L-II] were observed at +0.09 and -1.20 V vs. Ag-AgCl, respectively. Thes e potentials are quite similar to those for [Co(salen)]. The electro-genera ted [(Co2L)-L-I](2-) reacts with alkyl halide at each metal center to give an organocobalt complex. A further one-electron reduction of the compound y ields an unstable intermediate that undergoes rapid decomposition by cleava ge of the cobalt-carbon bond. The electrolysis of benzyl bromide at -1.40 V vs. Ag-AgCl in the presence of the dicobalt complex yields bibenzyl as the major product. On the other hand, when [Co(salen)] was used as a catalyst, toluene was obtained as the major product. The difference in the product d istribution is due to the structural properties of the catalysts.