Abstract
A priority task in contemporary organic chemistry consists in the synthesis of practically useful metal complexes having carbonyl-containing ligands. The present article details the isolation of several new bis-(4-alkyl(aryl)-1-oxo-1-alkoxyalkane-2,4-dionato) metals (II) via complex formation of metal salts of (zinc (II), copper (II) and nickel (II)) with sodium 1-alkoxy-1,4-dioxo-2-alkenolates obtained by condensation of alkyl (aryl) methyl ketones with dialkyl oxalates in the presence of sodium or sodium hydride as a condensing reagent. The structure of the synthesised sodium oxoenolates and metal complexes was confirmed by spectral analysis methods (IR, NMR 1 H-, NMR 13 C-spectroscopy and mass spectrometry). In the IR spectra of the solid samples of the isolated compounds, stretching vibrations bands of ester carbonyl groups were identified, as well as high-intensity ether bands due to the vibrations of С-О-С bonds. For compounds containing aromatic fragments, bands corresponding to vibrations of monosubstituted benzene rings were found in the IR spectra. The NMR spectra of 1 H of sodium oxoenolates and metal complexes recorded in DMSO-d 6 demonstrated characteristic signals of ethoxy and n - butoxy fragments, methine protons, as well as protons of aromatic rings. Chemical shifts of carbon atoms in the NMR spectra 13 C of sodium oxoenolates correspond well to the reference values. In the mass spectra of synthesised compounds recorded in electrospray mode, signals of protonated and cationised molecules were observed [M+H] + , [M+NH 4 ] + , [M+Na] + , [M+K] + . Using quantum chemical methods, the models of the obtained compounds were constructed along with a calculation of the formation energies and dissociation constants. Optimisation of the geometric parameters of the equilibrium states of sodium oxoenolate and metal complexes was carried out using the following two methods: density functional theory (DFT) and self-consistent field (SCF). The relative formation energies indicate high stability of the synthesised substances, while, according to the data obtained, copper complexes are characterised by greater stability in the gas phase as compared to zinc and nickel.
Highlights
The chemistry of metal complexes is an extensive and rapidly developing field due to the multifunctionality and practical significance of these materials
Among metal complexes having organic ligands, the least studied are those based on polycarbonyl systems with conjugated α- and β-dioxo links
In order to expand the number of available metal complexes having carbonyl-containing ligands, the present study set out to synthesise new representative compounds and evaluate their stability using quantum chemical methods
Summary
The chemistry of metal complexes is an extensive and rapidly developing field due to the multifunctionality and practical significance of these materials. In order to expand the number of available metal complexes having carbonyl-containing ligands, the present study set out to synthesise new representative compounds and evaluate their stability using quantum chemical methods. A solution of 1.0 mmol (0.18 g) zinc acetate, 1.0 mmol (0.18 g) of copper acetate or 1.0 mmol (0.24 g) of nickel chloride hexahydrate in 30–50 ml of water was added with stirring to a solution of 2.0 mmol of sodium 4-alkyl(aryl)-1alkoxy-1,4-dioxo-2-alkenolates (1а or 1b) in 30–50 ml of water for preparation of compounds 2а and 2d, 2b and 2e, 2c and 2f, correspondingly. The optimisation of the geometric parameters of the equilibrium states of sodium oxoenolate and metal complexes was carried out using the following two methods: density functional theory (DFT) and self-consistent field (SCF). The calculations were performed in the FireFly 8.1 software package
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