ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ
Mono- and mixed-ligand complexes of La (III) with aliphatic β-ketoesters were synthesized in the solid state. The complexes have the general formulas LаL2OH·H2O (L=meacac, etacac, alacac) and La(meacac)2X·nCH3OH(X = NO3, CH3COO; n = 1, 2). Their composition, structure, and thermal propertie...
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| Datum: | 2021 |
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| Sprache: | Englisch |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2021
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| Online Zugang: | https://ucj.org.ua/index.php/journal/article/view/343 |
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| Назва журналу: | Ukrainian Chemistry Journal |
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Ukrainian Chemistry Journal| _version_ | 1856543774493114368 |
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| author | Mishchenko , Artem Trunova , Elena Makotryk , Tamara |
| author_facet | Mishchenko , Artem Trunova , Elena Makotryk , Tamara |
| author_sort | Mishchenko , Artem |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2022-03-30T17:10:50Z |
| description | Mono- and mixed-ligand complexes of La (III) with aliphatic β-ketoesters were synthesized in the solid state. The complexes have the general formulas LаL2OH·H2O (L=meacac, etacac, alacac) and La(meacac)2X·nCH3OH(X = NO3, CH3COO; n = 1, 2). Their composition, structure, and thermal properties were established by chemical and thermal analysis, IR spectroscopy. It is shown that β-ketoesters are coordinated to the La (III) ion bidentate-cyclically into monoligand hydroxocomplexes. Ligand complexes with methylacetoacetate have an oligomeric structure. They consist of cationic fragments [La(meacac)2]+ with bridged connection of the nitrate or acetate anions.
The thermal destructions of LaL2OH·H2O (L = meacac, etacac, alacac), La(meacac)2NO3· 2CH3OH and La(meacac)2(CH3COO)·CH3OH were studied for the first time in the helium dynamic atmosphere by TGA-MS in the temperature range of 25–900 °C. Depending on the ligand, dehydratation of the hydroxo-complexes takes place in the 120–180 (meacac), 120–190 (etacac) or 110–160 °C (alacac) temperature range, and the mass loss corresponds with the detachment of one water molecule. Decomposition of mixed-ligand complexes starts with the detachment of methanol in the 60–100 °C range. For La(meacac)2NO3·2CH3OH the decomposition process is attended with oxidation of methanol to carbon dioxide due to reduction of the nitrate-ion to nitrogen dioxide. Further heating to 300–400 °C leads to destruction of organic parts of the complexes attended with the release of low-molecular oxygen-containing organic compounds (aldehydes, ketones, alcohols), carbon dioxide and water. At ~500 °C all the La(III) complexes under study totally decompose, yielding the oxycarbonate La2O2CO3, which was fixed by IR spectroscopy. Under further heating to 850 °С oxycarbonate gradually decomposes to La2O3 liberating CO2. |
| first_indexed | 2025-09-24T17:43:40Z |
| format | Article |
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-343 |
| institution | Ukrainian Chemistry Journal |
| language | English |
| last_indexed | 2025-09-24T17:43:40Z |
| publishDate | 2021 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-3432022-03-30T17:10:50Z THERMODESTRUCTION OF Lа(III) COORDINATION COMPOUNDS WITH ALIPHATIC β-KETOESTERS ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ Mishchenko , Artem Trunova , Elena Makotryk , Tamara lanthanum complexes, β-ketoesters, thermal analysis. Mono- and mixed-ligand complexes of La (III) with aliphatic β-ketoesters were synthesized in the solid state. The complexes have the general formulas LаL2OH·H2O (L=meacac, etacac, alacac) and La(meacac)2X·nCH3OH(X = NO3, CH3COO; n = 1, 2). Their composition, structure, and thermal properties were established by chemical and thermal analysis, IR spectroscopy. It is shown that β-ketoesters are coordinated to the La (III) ion bidentate-cyclically into monoligand hydroxocomplexes. Ligand complexes with methylacetoacetate have an oligomeric structure. They consist of cationic fragments [La(meacac)2]+ with bridged connection of the nitrate or acetate anions. The thermal destructions of LaL2OH·H2O (L = meacac, etacac, alacac), La(meacac)2NO3· 2CH3OH and La(meacac)2(CH3COO)·CH3OH were studied for the first time in the helium dynamic atmosphere by TGA-MS in the temperature range of 25–900 °C. Depending on the ligand, dehydratation of the hydroxo-complexes takes place in the 120–180 (meacac), 120–190 (etacac) or 110–160 °C (alacac) temperature range, and the mass loss corresponds with the detachment of one water molecule. Decomposition of mixed-ligand complexes starts with the detachment of methanol in the 60–100 °C range. For La(meacac)2NO3·2CH3OH the decomposition process is attended with oxidation of methanol to carbon dioxide due to reduction of the nitrate-ion to nitrogen dioxide. Further heating to 300–400 °C leads to destruction of organic parts of the complexes attended with the release of low-molecular oxygen-containing organic compounds (aldehydes, ketones, alcohols), carbon dioxide and water. At ~500 °C all the La(III) complexes under study totally decompose, yielding the oxycarbonate La2O2CO3, which was fixed by IR spectroscopy. Under further heating to 850 °С oxycarbonate gradually decomposes to La2O3 liberating CO2. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-09-24 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/343 10.33609/2708-129X.87.08.2021.99-115 Ukrainian Chemistry Journal; Vol. 87 No. 8 (2021): Ukrainian Chemistry Journal; 99-115 Украинский химический журнал; Том 87 № 8 (2021): Ukrainian Chemistry Journal; 99-115 Український хімічний журнал; Том 87 № 8 (2021): Український хімічний журнал; 99-115 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/343/182 |
| spellingShingle | Mishchenko , Artem Trunova , Elena Makotryk , Tamara ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ |
| title | ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ |
| title_alt | THERMODESTRUCTION OF Lа(III) COORDINATION COMPOUNDS WITH ALIPHATIC β-KETOESTERS |
| title_full | ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ |
| title_fullStr | ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ |
| title_full_unstemmed | ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ |
| title_short | ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ |
| title_sort | термодеструкція координаційних сполук la(iii) із аліфатичними β-кетоестерами |
| topic_facet | lanthanum complexes β-ketoesters thermal analysis. |
| url | https://ucj.org.ua/index.php/journal/article/view/343 |
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