Synthesis,characterization and biomimetic oxygenations of manganese(II), iron(III) and copper(II) pyridyl hydrazone complexes |
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Authors: | Ramadan Abd El-Mottaleb M El-Mehasseb Ibrahim M |
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Institution: | (1) Chemistry Department, Faculty of Education, Tanta University, Kafr El-Sheikh, Egypt |
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Abstract: | The preparation and characterization of MnII, FeIII and CuII complexes of three tridentate pyridyl hydrazones are reported.
The ligands were prepared via Schiff base condensation of 6-chloro-2-hydrazopyridine with alpha-formyl-(L1), alpha-acetyl-(L2),
or alpha-benzoyl-(L3) pyridine. The structural characterization of the compounds prepared was based on elemental analyses,
electrical conductance and magnetic moment measurements, 1H-n.m.r., i.r., u.v.-vis. and e.s.r spectroscopic methods. The overall
structure and reactivity of the metal chelates critically depend on the ligand substituents within the carbonyl moiety. Octahedral
and tetrahedral monomeric species were proposed for MnII complexes, and an octahedral environment for the FeIII complexes.
Regarding the copper(II) complexes, a monomeric square-planar and a dimeric structure with a chloride bridge in square-pyramidal
geometry were suggested. In the presence of molecular oxygen, MnII and CuII complexes catalyse the oxidative transformation
of catechol (benzene-1,2-diol) to the corresponding o-benzoquinone. Iron(III) complexes catalyse the aerobic oxidation of
catechol to the intradiol cleavage product. The catalytic activity has been correlated with the Lewis acidity of the metal
centres created according to the nature of the ligand substituents. The probable mechanistic implications of the catalysed
oxidation reactions are discussed.
This revised version was published online in June 2006 with corrections to the Cover Date. |
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