Synthesis and structure of sodium 1-alkoxy-1,4-dioxo-2-alkenolates and bis-(4-alkyl(aryl)- 1-oxo-1-alkoxyalkane-2,4-dionato) metals (II) based on them
https://doi.org/10.21285/2227-2925-2020-10-2-180-187
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 1H-, NMR 13C-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 1H of sodium oxoenolates and metal complexes recorded in DMSO-d6 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 13C 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+NH4]+, [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.
About the Authors
E. A. Kunavina
Orenburg State University
Russian Federation
Cand. Sci. (Chemistry), Associate Professor
13, Pobedy Ave., Orenburg, 460018, Russian Federation
Russian Federation
Cand. Sci. (Chemistry), Associate Professor
13, Pobedy Ave., Orenburg, 460018, Russian Federation
S. A. Peshkov
Orenburg State University
Russian Federation
Cand. Sci. (Chemistry), Associate Professor
13, Pobedy Ave., Orenburg, 460018, Russian Federation
Russian Federation
Cand. Sci. (Chemistry), Associate Professor
13, Pobedy Ave., Orenburg, 460018, Russian Federation
A. Yu. Iskandarov
Tashkent State Pedagogical University
Uzbekistan
Associate Professor, Department of Chemistry and Methodology of Teaching Chemistry
27, Bunyodkor Ave., Tashkent, 100183, Uzbekistan
Uzbekistan
Associate Professor, Department of Chemistry and Methodology of Teaching Chemistry
27, Bunyodkor Ave., Tashkent, 100183, Uzbekistan
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Review
For citations:
Kunavina E.A., Peshkov S.A., Iskandarov A.Yu. Synthesis and structure of sodium 1-alkoxy-1,4-dioxo-2-alkenolates and bis-(4-alkyl(aryl)- 1-oxo-1-alkoxyalkane-2,4-dionato) metals (II) based on them. Proceedings of Universities. Applied Chemistry and Biotechnology. 2020;10(2):180-187. https://doi.org/10.21285/2227-2925-2020-10-2-180-187
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