Abstract
New oxo-centered trinuclear mixed-metal complex, of [Fe2ZnO(CHCl2CO2)6(CHCl2CO2)3].NO3 was synthesized by the direct reaction between metal nitrates and dichloroacetic acid. These compounds have a typical μ3-oxo trinuclear structure: (a) three metal atoms are situated in the apexes of the equilateral triangle; (b) μ3-oxygen atom and six dichloroacetate ligands fulfil the bridge functions and (c) the monodentate CHCl2CO2 ligands complete the octahedral geometry of the metal ions. This complex were characterized by elemental analyses (CHN), atomic absorption spectroscopy and spectral (IR, electronic) studies. This is new types of oxo-bridged mixed-metal complex in which the carboxylate ligand is dichloroacetic acid. The UV spectra of the complex exhibited strong bands in the region 213 and 257 nm which are related to the (π → π*) and (n → π*) transitions of the CHCl2CO2 ligands, respectively. The IR spectra of this compound showed two strong stretching vibrations bands, indicating a bridging coordination mode of the carboxylic group by presence of νasym (M2M'O) vibrations of the ligand in the infrared spectra. KEY WORDS: Oxo-centered, Trinuclear complexes, Carboxylic ligand, Crystallographic data, IR spectra Bull. Chem. Soc. Ethiop. 2018, 32(3), 491-500.DOI: https://dx.doi.org/10.4314/bcse.v32i3.8
Highlights
Transition-metal carboxylate chemistry has played a key role in the conceptual development of modern inorganic chemistry [1]
The current interest in the trinuclear, oxo-centered metal carboxylate assemblies of the general composition [M3O(OOCR)6L3]+ (where M = trivalent 3-d metal, RCOO = carboxylic acid (R = CH3, Ph, etc) L = monodentate ligand) is due to these complexes have served as important models to test theories of magnetic and electronic coupling between metal ions [2, 3]
There is interest in establishing how substitution in the carboxylate bridge affects the liability of the terminal ligand and the redox potential of the metal centers. These carboxylate complexes are of additional interest when the carboxylate is unsaturated, because there is a potential scope for further polymerization in the solid state by cross-linking of the substituents [6, 7]
Summary
Transition-metal carboxylate chemistry has played a key role in the conceptual development of modern inorganic chemistry [1]. We reported fabrication of some trinuclear oxo-centered complexes with saturated and unsaturated carboxylate ligands [10,11,12,13,14]. Metal coordination spheres are slightly deformed octahedra (Table 1); oxygens from four bridging dichloroacetate (DCA) moieties form the equatorial plane, while the axial ligands are a terminal monodentate DCA and the central oxide dianion (Figure 2).
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