Electrochemical and spectroscopic characterization of new cobalt(II) complexes.: Catalytic activity in oxidation reactions by molecular oxygen

The synthesis and characterization of some new complexes with tetradentate Schiff bases derived from bis(salicylaldehyde)etylenediimine, H(2)Salen are reported in this paper. The Co(II) Schiff bases complexes investigated are: (bis(5-nitro-salicy-laldehyde) ethylenediiminato)cobalt(II), (CoNSalen); (bis(a-ethyl-salicylaldehyde) ethylenediiminato)cobalt(II) (CoEtSalen); (bis(alpha -ethyl-3,5-diiode-salicylaldehyde) ethylenediiminato) cobalt(II),(CoDIEtSalen); (bis(alpha ,5-dimethyl-3-iode-salicylaldehyde)ethylenediiminato)cobalt(II) (CoDMISalen) and (bis(salicylaldehyde)methylene-p,p ' -diphenytene)cobalt(II), (CoSalmbfn). The characterization of the complexes was performed by elemental analysis, UV-Vis, FTIR spectroscopy, powder X-ray diffraction and cyclic voltammetry. Pyridine (py), present in the solution of complexes in DMF, coordinates to the metal ion in axial position, inducing a significant decrease of the redox potentials. Significant influences have the substituents grafted on ligands molecules. The separated complexes evince catalytic activity in the oxidation reaction of 2,6-di-t-butylphenol with molecular oxygen. These complexes seem capable to form reversible adducts with molecular oxygen. (C) 2001 Elsevier Science B.V. All rights reserved.