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PAPERS IN ENGLISH
CHEMISTRY SCIENCES
INORGANIC CHEMISTRY
SYNTHESIS AND ANALYSIS OF THE COORDINATION COMPOUND OF Co(II) OXALATE
WITH CALCIUM ACETATE
Dinora Zaripova
PhD student, Khorezm Mamun Academy, Uzbekistan, Khiva E-mail: [email protected]
Zubayda Abdullaeva
Associate Professor, Urgench RANCH University of Technology, Uzbekistan, Urgench E-mail: [email protected]
Shakhnoza Kadirova
Professor,
National university of Uzbekistan, Uzbekistan, Tashkent
СИНТЕЗ И АНАЛИЗ КООРДИНАЦИОННОГО СОЕДИНЕНИЯ ОКСАЛАТ CO(II)
С АЦЕТАТОМ КАЛЬЦИЯ
Зарипова Динора Ибрагимовна
аспирант
Хорезмской академии Мамуна, Республика Узбекистан, г. Хива
Абдуллаева Зубайда Шавкатовна
доцент,
Ургенчский технологический университет RANCH, Республика Узбекистан, г. Ургенч
Кадирова Шахноза Абдухалиловна
профессор,
Национальный университет Узбекистана, Республика Узбекистан, г. Ташкент
ABSTRACT
Calcium acetate of Co(II) oxalate the synthesis of the complex compound with factors affecting the synthesis of the resulting complex compound in room conditions were shown. The element composition of the synthesized complex was analyzed. The complex compound was studied using IR-spectroscopic and thermal analysis methods, and its chemical structure, coordination bond formation and thermal stability were determined. It was also proved that the complex compound is thermally and chemically stable.
Библиографическое описание: Zaripova D., Abdullaeva Z., Kadirova Sh. SYNTHESIS AND ANALYSIS OF THE COORDINATION COMPOUND OF Co(II) OXALATE WITH CALCIUM ACETATE // Universum: химия и биология : электрон. научн. журн. 2024. 11(125). URL: https://7universum.com/ru/nature/archive/item/18520
АННОТАЦИЯ
Показан синтез комплексного соединения ацетата кальция с оксалатом Со (II) и факторы, влияющие на синтез полученного комплексного соединения в комнатных условиях. Проанализирован элементный состав синтезированного комплекса. Методами ИК-спектроскопии и термического анализа изучено комплексное соединение, определены его химическая структура, образование координационных связей и термическая устойчивость. Доказано, что комплексное соединение термически и химически стабильно.
Keywords: Cobalt(II) acetate, oxalic acid, calcium acetate, complex compound, infrared spectroscopy, differential scanning colorometry
Ключевые слова: Ацетат кобальта(П), щавелевая кислота, ацетат кальция, комплексное соединение, инфракрасная спектроскопия, дифференциальная сканирующая колорометрия.
Introduction. The study of coordination compounds allows to explain their main chemical properties, to form complexes, to determine the nature of chemical bonds between ligands, to determine the mechanisms of processes involving coordination compounds and changes in the reactivity of coordinated ligands using modern physical research. The information obtained is important for the targeted search and synthesis of new chemical substances with predetermined properties, composition and structure, as well as other important properties [1, 2]. This is particularly necessary for substances with biologically active properties that are used in medicine [3]. Enzymes that function in the human body are also complex chemical compounds [5]. When poisoned with metals, they are treated by changing them into complex compounds and eliminating them from the body [6].
The authors of [7] demonstrated the possibility of using heterometallic pivalate [Co2Sm(Piv)7(2,4-Lut)2] as a SmCoO3 precursor. In contrast to the previously discussed works, the authors determined the structure of the resulting complex. A comprehensive study (DSC and TGA with mass spectral analysis of gaseous products) of the thermolysis of the obtained compound in an inert atmosphere (dried Ar) and artificial air atmosphere was carried out. The solid product of thermolysis in air is a mixture of SmCoO3 and Co3O4 (XRD), which is explained by the initial excess of Co atoms (compared to the 1:1 stoichiometry required to form pure SmCoO3). A completely different character of decomposition was observed in an inert atmosphere. In this case, the volatile [Co8^4-O)2^2-OOCCMe3M^-OOCCMe3)6] is removed before the final solid product is formed; thus, the Sm:Co ratio in the solid decomposition product is optimal for the formation of single-phase SmCoO3.
As mentioned above, one of the main advantages of precursor methods for the preparation of complex oxides is the ability to control the ratio of heterometallic atoms at the synthesis stage of a given precursor complex. Thus, in [8], the use of 2,2'-bipyridyl (bpy) as a structure-forming ligand in the synthesis of heterometallic 3d-4f pivalate complexes [(bpy)CoLn(Piv)5(H2O)], [(bpy)NiLn(Piv)5(H2O)] and [(bpy)CuLn(Piv)5(HPiv)]
(Ln = Sm, Gd), i. e., the ratio of heterometallic atoms is optimal (to later obtain MLnO3). The resulting compounds will be fully characterized. The synthesis methodology developed in [9] proved to be very convenient and versatile, allowing it to be applied to the pivalate synthesis of other lanthanides with other N-donor ligands (in particular 1,10-phenanthroline): [MLn(Piv)s(fen)] (M=Co, Cu, Zn; Ln= Eu, Gd). A detailed study of the solid phase thermolysis of all the complexes under different conditions was carried out. A comparative analysis of the thermolysis of bihedral heterometallic complexes with a metal carboxylate framework {MLn(piv)5} in oxidising environments was carried out, and the influence of the d-metal nature on the decomposition temperature of the metal framework of the same ligand complexes was shown. It was found that the introduction of the non-volatile N-donor ligand 1,10-phenanthroline into the complex leads to an increase in the starting temperature of the oxidative degradation of the metal carboxylate skeleton, but has almost no effect on the temperature at which the formation of solid thermolysis products ends. Solid-phase thermolysis in air leads to the formation of single-phase cobaltites (LnCoO3) in Co-containing complexes, a mixture of phases in Cu-containing complexes (Ln2CuO4 and CuO), and mixtures of common ligand and NiO oxides in Ni complexes. The use of the [(bpy)CoSm(Piv)s(H2O)] complex has been shown to allow the preparation of ultrathin monophase SmCoO3, the magnetic properties of which have been studied.
Research methodology. Calcium acetate and cobalt (II) oxalate salts of the 'pure for analysis' brand were used for the synthesis of complex compounds.
The following method was used to synthesize Co(II) oxalate acetate calcium complex compound: an aqueous solution of Co oxalate (0.001 mol) and an aqueous solution of Ca acetate (0.002 mol) were mixed with a magnetic stirrer at a speed of 800 revolutions at a temperature of 400C for 1 hour. At first, the solution turned dark red, then pink, and was left at room temperature for 15 days. As a result, Co(II) oxalate acetate Ca complex was formed [10].
Analysis and results. Elemental analysis of synthesized compounds andmicrostructure was determined using an Aztec Energy Advanced X-Act (Oxford) instrument brand scanning electron microscope SEM-EVO-MA 10 (Zeiss) energy dispersive X-ray spectrometer. Determining the amount of elements
in substances using a scanning electron microscope (SEM) is widely used in solving specific scientific and technological problems due to the high information content and reliability of the obtained research results for the analysis of materials [11].
Table 1.
The results of the elemental analysis of the complex compound formed by Co(II) oxalate with calcium acetate
Compound Co % C, % Ca % O, %
Found Calculated Found Calculated Found Calculated Found Calculated
[CoC2O4-Ca(CH3COO)d 19.34 21.64 19.67 20.2 13.1 14.9 41.96 43.7
In order to determine the coordination centers and coordination paths of the synthesized compounds, the synthesized compounds were analyzed by IR-spectroscopic method (Fig. 1).
As a result of the analysis of the coordination compound formed by Co (II) oxalate with Ca acetate, comparing it with the IR spectrum of the original substances, it was found that changes occurred in the IR spectrum of the new substance. The main changes were observed in the Co-O bond, and there were also changes in the asymmetric and symmetric acetate group vibrations.
In cobalt oxalate, the vibration frequency of the CoO bond is observed at 476 cm-1, after coordination, the vibration frequency increases and moves to 493 cm-1. In calcium acetate, the vibrational frequency of 638 cm-1,
which is typical for the Ca-O bond, shifts to the 671 cm-1 region in the complex compound.
Asymmetric and symmetric vibrations of the acetate anion vs(COO-)=1447 cm-1 and vas(COO-)=1531 cm-1 was observed. Changes in the vibration fields are observed when moving to the coordinated state, vs(COO-)=1368 cm-1, changed to v4COO-)=1556 cm-1. This corresponds to bidentate-bridged coordination and indicates that the acetate anion forms a bridged bond with the central atom. Another evidence proving the presence of the acetate group in the synthesized compounds is the presence of deformational and valence vibrations of the methyl group in the absorption region at 1031 cm-1 in the IR spectrum of the synthesized compound (Table 1).
Figure 1. IR-spectrum of the compound [(CoC2O4)2Ca(CH3COO)2] Characteristic frequencies of absorption in IR spectra of coordination compound
Table 2.
No Compounds 8(M-0) vs(COO-) 1300-1420 cm-1 Vas(COO-) 1500-1600 cm-1 8(-CT3) 1013-1076 cm-1
1 (CoC2O4)2 476 1391 1565 -
2 Ca(CHsCOO)2 638 1447 1531 1056
3 [(CoC2O4)2-Ca(CHsCOO)2] 493 671 1368 1556 1031
The thermal stability of the synthesized complex compound was analyzed based on the results of derivatographic analysis of various exothermic and endothermic heat effects observed with mass change as a result of destruction.
In the derivatogram of [(CoC2O4^Ca(CH3COO)2] complex, three endothermic effects were observed at temperatures of 136, 155, 220oC and two exothermic effects at temperatures of 185, 285oC. At a temperature
of 136oC, the first endoeffect complex begins to decompose. The exoeffect at 1850C is due to the combustion of thermolysis products, and at 220oC the decomposition of acetic and oxalic acid residues is completed. The exothermic observation at 285oC can be explained by the burning of thermolysis products of metal and ligands and the formation of the last product - metal oxide. The total mass reduction in the temperature range of 30-400oC was 62.2% (Fig. 2).
Figure 2. Derivatogram of [(CoC2O4)rCa(CH3COO)2]
Conclusion. As a result of elemental analysis, it was determined that in the composition of Co(II) oxalate acetate calcium complex compound, the initial substances are in a ratio of 1:2. It was proved that the coordination compound formed as a result of IR-spectroscopic analysis is a polynuclear heterometallic complex compound. In this case, the coordination bond is realized through bidentate-bridged coordination
of acetate groups.The synthesized coordination compound decomposes at a relatively low temperature. In this case, the maximum mass loss is not more than half of the sample mass, and no mass change is observed after 400oC. Based on this, it can be concluded that the ligands are connected directly by the coordination bond and are located in the inner sphere, and this weak bond breaking occurs at a relatively low temperature.
References:
1. Zadesenets A.V., Garkul I.A., Filatov E.Y., Plyusnin P.E., Filippov T.N., Asanova T.I., Korolkov I.V., Baidina I.A., Asanov I.P., Korenev S.V. Oxalate complexes of Pd(II) with Co(II) and Ni(II) as single-source precursors for bimetallic nanoalloys // J. Therm. Anal. Calorim. 2019. Vol. 138. P. 111-121.
2. Garkul I., Zadesenets A., Filatov E., Baidina I., Tkachev S., Samsonenko D., Korenev S. Oxonium trans-bis(oxalato) rhodate and related sodium salts: a rare example of crystalline complex acid // Acta Crystallogr. Sect. B. 2021. Vol. 77. № 6. P. 1048-1054.
3. Zadesenets A.V., Garkul I.A., Filatov E.Y., Sukhikh A.S., Plusnin P.E., Urlukov A.S., Uskov S.I., Potemkin D.I., Korenev S.V. Double oxalates of Rh(III) with Ni(II) and Co(II) - effective precursors of nanoalloys for hydrocarbons steam reforming // Int. J. Hydrog. Energy. 2023. DOI:10.1016/j.ijhydene.2023.01.365
4. A. Zadesenets, I. Garkul, P. Plusnin, I. Baidina, S. Korenev. Oxalatopalladates cobalt and nickel as precursors of nanoalloys: from thermal properties to supported catalysts // 27th International Chugaev Conference on Coordination Chemistry (Нижний Новгород, 2017).
5. Задесенец А.В., Гаркуль И.А., Коренев С.В. Oxalatopalladates of Co, Ni and Zn as precursors of nanoalloys: from thermal properties to supported catalysts // The Twentieth Annual Conference YUCOMAT (Херцег-Нови, Черногория, 2018).
6. Carp, O. Thermal properties of solid coordination compounds. IV. Some applications in materials science / Oana Carp, Luminita Patron, Eugen Segal // Rev. Roum. Chim.-2006.-V.51.-pp 5-12.
7. Patron, L. Thermal behaviour of some polyhydroxycarboxylic coordination compounds with neodium / L. Patron, O. Carp, I. Mandru, G. Grasa // J. Therm. Anal. Calor.-1999.-V.56.-pp. 597-602.
8. Carp, O. Influence of precursor on the thermally induced synthesis dysprosium manganite with perovskite structure / O. Carp, L. Patron, A. Ianculescu, D. Crisan, N. Dragan, R. Olar // J. Therm. Anal. Calor.-2003.-V.72.-pp. 253-261.
№ 11 (125)_¿Y^ химия и биология_ноябрь. 2024 г.
9. Sh.A. Kadirova, Z.Sh. Abdullaeva, Sh.B. Khasanov, Sh.B. Kurambaeva. Koordinasionnie soedineniya formiata kobalta (II) s atsetatami ammoniya i kaltsiya [Coordination compounds of cobalt (II) formate with ammonium and calcium acetates] // Current issues of modern science and education, - 2020. - P. 11 [In Russian]
10. Sh.A. Kadirova, Z.Sh. Abdullaeva, Sh.B. Khasanov. Sintez i issledovanie koordinasionnix soedineniy formiata medi (II) s atsetatami metallov [Synthesis and study of coordination compounds of copper (II) formate with metal acetates] // Universum: chemistry and biology, -2020. - No. 1(67). P. 36-38 [In Russian]
11. Zeer G.M., Fomenko O.Yu., Ledyaeva O.N. Primeneniye skaniruyushchey elektronnoy mikroskopii v reshenii aktual'nykh problem materialovedeniya [Application of scanning electron microscopy in solving current problems in materials science] // Journal of the Siberian Federal University. - 2009. - V.2. - No. 4. - P. 287-293. [In Russian]
