Author:
Amirnasr Mehdi,Vafazadeh Rasoul,Mahmoudkhani Amir H
Abstract
A series of complexes of the type trans-[Co((BA)2en)(amine)2]ClO4 where (BA)2en is the bis(benzoylacetone)ethylenediimine dianion and the amines are morpholine (mrpln) 1, aniline (aniln) 2, benzylamine (bzlan) 3, piperidine (pprdn) 4, p-toluidine (p-toldn) 5, and pyrrolidine (prldn) 6 has been synthesized and characterized by elemental analysis, UVvis, 1H NMR, and 13C NMR spectroscopy. The crystal and molecular structure of trans-[Co((BA)2en)(mrpln)2]ClO4 (1) has been determined by X-ray crystallography. The electrochemical reduction of these complexes at a glassy-carbon electrode, in the potential range of 0.5 to 2.0 V (vs. Ag/AgCl), in acetonitrile solution, indicates that the first reduction potential of Co(III/II) is irreversible, which is accompanied by the dissociation of the axial aminecobalt bonds. This potential is dependent on the pKa of the axial amines. The second reduction potential of Co(II/I) shows reversible behavior and is also independent of the axial amine pKa. These results indicate the loss of the axial amines in the first redox process and the involvement of a four-coordinate species in the second redox step.Key words: Schiff base, cobalt(III), axial amine, electrochemical properties, crystal structure.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
28 articles.
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