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Synthesis,Characterization, and Electrochemical Properties of a Novel Macrocylic Ligand and its Transition Metal Complexes
Authors:İsmail Yılmaz  Mehmet Kandaz  Ali Riza Özkaya  Atıf Koca
Affiliation:1.?Department of Chemistry, Technical University of ?stanbul, TR-80626 Maslak, ?stanbul, Turkey,TR;2.?Department of Chemistry, Sakarya University, TR-54100 Adapazar?, Sakarya, Turkey,TR;3.?Department of Chemistry, Marmara University, TR-81040 Kad?k?y, ?stanbul, Turkey,TR
Abstract:Summary.  2,3-Dibromo-6,7,13,14,15,16,22,23-octahydro-14,15-bis-(hydroxyimino)-tribenzo [e,k,q][1,4,7,10,13,16]tetraoxadiazacyclohexadecine (LH4) was prepared by condensation of 1,2-bis-(2′-aminophenoxyethoxy)-4,5-dibromobenzene with cyanogen-di-N-oxide. Mono-, di-, and trinuclear transition metal complexes of this ligand ((LH3)2Ni, (LH3)2Zn, (LH3)2Co, (LH3)2Cu, (LH3)2Fe, (LH3)2(UO2)2(OH)2, (LH)2Cu3, (LH)2Co3) were synthesized under basic conditions. The electrochemical properties of the mono- and dinuclear complexes were studied by cyclic voltammetry in DMSO solution containing TBAP. The results showed that all redox processes are based on the metal center and the oxime ligands stabilize the Ni(III), Fe(III), Co(III), and Cu(III) species formed during oxidation. The Fe(II) and U(VI)O2 complexes displayed a different behaviour: a reduction peak with the corresponding anodic signal during the reverse scan was observed. The oxime moiety also stabilizes U(V)O2 which forms during the reduction process of the uranyl complex. Cu(II) was adsorbed on the electrode surface upon scanning cathodically. Received August 20, 2001. Accepted (revised) October 17, 2001
Keywords:.   vic-Dioxime   Macrocycle   Co(II)   U(IV)   Electrochemistry.
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