Spectral and electrochemical study of coordination molecules Cu4OX6L4: 3-Methylpyridine and 4-Methylpyridine Cu4OBrnCl(6−n)L4 complexes
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G. Ondrejovič
und
A. Kotočová
Abstract
The tetranuclear Cu4OBrnCl(6-n)L4 complexes, where L = 3-methylpyridine (3-Mepy), 4-methylpyridine (4-Mepy) and n=0–6 with trigonal bipyramidal coordination of copper(II) were prepared and their infrared and electronic absorption spectra as well as cyclic voltammograms in nitromethane solutions were measured. The polyhedra in Cu4OBrnCl(6−n) (3-Mepy)4 molecules are less distorted comparing with those of 4-Mepy analogues as indicated by infrared Cu4O absorptions, far infrared Cu—Br, Cu—Cl, and Cu—N absorptions, d—d bands in electronic spectra and potentials, measured by cyclic voltammetry. The 3-Mepy complexes exhibit strong single infrared Cu4O absorptions, while for related 4-Mepy complexes doubly split Cu4O bands were observed. Two strongly overlapped d—d bands in electronic absorption spectra of the 3-and 4-Mepy complexes in nitromethane were resolved by Gaussian fitting. The 4-Mepy ligand produces slightly stronger ligand field than its 3-Mepy analogue. The maxima of high-energy d—d bands are in a linear correlation with the number of bromide ligands. The correlations for corresponding low-energy bands are considerably deviated from linearity. The halfwave potentials of the complexes in nitromethane correlate with both the number of bromides and the data of electronic absorption spectra suggesting that the reducing electron at the electrode process enters the half-filled d z 2 orbital of the copper(II) atom. The origin of a difference between the 3-and 4-Mepy complexes in their spectral and electrochemical properties is also discussed.
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© 2006 Institute of Chemistry, Slovak Academy of Sciences
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Artikel in diesem Heft
- Carbon dioxide production in the oscillating Belousov—Zhabotinsky reaction with oxalic acid
- Potentiometric and thermodynamic studies of 3-methyl-1-phenyl-{p-[N-(pyrimidin-2-yl)-sulfamoyl]phenylazo}-2-pyrazolin-5-one and its metal complexes
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- Anodic stripping voltammetric determination of lead and cadmium in soil extracts
- Gold and silver determination in Waters by SPHERON® Thiol 1000 preconcentration and ETAAS
- Syntheses, geometry optimization, and electronic structure of N-and C-substituted benzonaphthyridines
- Synthesis, spectral description, and lipophilicity parameters determination of phenylcarbamic acid derivatives with integrated N-phenylpiperazine moiety in the structure
- New methods in synthesis of acetylcholinesterase reactivators and evaluation of their potency to reactivate cyclosarin-inhibited AChE
- Furan-containing thiacyanine analogs and their antimicrobial activity
- Synthesis and biological activity of new 1,3,4-thiadiazole derivatives
- Synthesis and identification of immunogen medroxyprogesterone acetate residues in edible foods and preparation of the Antisera
- Synthesis and characterization of oligosalicylaldehyde-based epoxy resins
- Extracellular polysaccharides produced by acapsular mutant of Cryptococcus laurentii
- Liquid chromatography of synthetic polymers under limiting conditions of insolubility. I. Principle of the method
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