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
Hauptverfasser: Mishchenko , Artem, Trunova , Elena, Makotryk , Tamara
Format: Artikel
Sprache:English
Veröffentlicht: V.I.Vernadsky Institute of General and Inorganic Chemistry 2021
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
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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
institution Ukrainian Chemistry Journal
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datestamp_date 2022-03-30T17:10:50Z
collection OJS
language English
topic_facet lanthanum complexes
β-keto­esters
thermal analysis.
format Article
author Mishchenko , Artem
Trunova , Elena
Makotryk , Tamara
spellingShingle Mishchenko , Artem
Trunova , Elena
Makotryk , Tamara
ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ
author_facet Mishchenko , Artem
Trunova , Elena
Makotryk , Tamara
author_sort Mishchenko , Artem
title ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ
title_short ТЕРМОДЕСТРУКЦІЯ КООРДИНАЦІЙНИХ СПОЛУК La(III) ІЗ АЛІФАТИЧНИМИ β-КЕТОЕСТЕРАМИ
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_sort термодеструкція координаційних сполук la(iii) із аліфатичними β-кетоестерами
title_alt THERMODESTRUCTION OF Lа(III) COORDINATION COMPOUNDS WITH ALIPHATIC β-KETO­ESTERS
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.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2021
url https://ucj.org.ua/index.php/journal/article/view/343
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