CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ

CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ

New heterometallic f-d-complexes of Pr (III), Co(II), Zn(II) with aminopolycarboxylic acids (ethylenediaminetetraacetic, ethylenediaminedisuccinic acids) have been synthesized and spectroscopically characterized. It was found that complexes with a molar ratio of Pr:M3d: EDTA=1:2:2 are formed for eth...

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Datum:2021
Hauptverfasser: Trunova , Elena, Mishchenko , Artem, 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/286
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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-2862021-05-13T15:14:04Z SYNTHESIS AND SPECTRAL CHARACTERISTICS OF HETEROMETALLIC COMPLEXES OF Pr(III) WITH Zn(II), CO(II) BASED ON ETHYLENEDIAMINETETRAACETIC AND ETHYLENEDIAMINEDISUCCINIC ACIDS CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ Trunova , Elena Mishchenko , Artem Makotryk , Tamara heterometallic complexes, praseodymium, 3d-metals, aminopolycarboxylic acids. New heterometallic f-d-complexes of Pr (III), Co(II), Zn(II) with aminopolycarboxylic acids (ethylenediaminetetraacetic, ethylenediaminedisuccinic acids) have been synthesized and spectroscopically characterized. It was found that complexes with a molar ratio of Pr:M3d: EDTA=1:2:2 are formed for ethylenediaminetetraacetic compounds, and that in the case of complexes based on EDDS, heteronuclear compounds of the equimolar composition Pr: M3d: EDDS = 1: 1: 1 are formed. It is shown that it is expedient to carry out the synthesis of heterometallic complexes on the basis of mono­nuclear polycarboxylates of 3d metals, which act as a «building block» for the preparation of a heterobinuclear compound by the exo coordination of additional metal ions. The complexes are characterized by the method of electron absorption spectroscopy. It is shown that independent of 3d-metal, for both heterometallic systems based on EDDS, a hypsochromic shift of the absorption maxima relative to νmax is observed for the homonuclear praseodymium complex. For ethylenediaminetetraacetate systems, the absorption maxima undergo both low- and high-frequency shift, which indicates the different nature of the ligand field effect, which is caused primarily by differences in the structure of the corresponding heteronuclearaminopolycarboxylates due to the presence of a chiral carbon atom in the EDDS molecule. For the supersensitive transitions Pr(III)) 3H4 →3P2 and 3H4 → 1D2 , the covalence parameters of the Ln-O bond have been calculated: osci­llator power (P), nepheloxetic parameter (β), covalence parameter (b1/2), Sinha parameter (δ). Analysis of the spectroscopic parameters indicates a decrease in the covalence of the lanthanide-ligand bond in the transition from mono- to heteronuclear complex, and a decrease in the local symmetry of the lanthanide ion occurs in the order Ln (III) aqua ion <hete­rometallic complex <monometallic complex. Heteronuclear complexes are several orders of magnitude more stable than mononuclear ones due to the formation of additional bonds or metallacycles with donor ligand atoms. It is noted that the stability of complexes with EDDS is lower than that of the corresponding complexes with EDTA due to the different size and number of chelated metallacycles. The obtained heteronuclear complexes belong to folded complexes, in which the ligand-complexone realizes the maximum denticity to the lanthanide ion, and the coordination sphere of the 3d-cation is formed by carboxyl groups EDTA / EDDS and inner-sphere water molecules. In this case, the ions of 3d-metals are in a distorted octahedral environment, and the coordination number of Pr(III) is 8. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-04-23 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/286 10.33609/2708-129X.87.03.2021.3-17 Ukrainian Chemistry Journal; Vol. 87 No. 3 (2021): Ukrainian Chemistry Journal; 3-17 Украинский химический журнал; Том 87 № 3 (2021): Ukrainian Chemistry Journal; 3-17 Український хімічний журнал; Том 87 № 3 (2021): Український хімічний журнал; 3-17 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/286/158
institution Ukrainian Chemistry Journal
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datestamp_date 2021-05-13T15:14:04Z
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language English
topic_facet heterometallic complexes
praseodymium
3d-metals
aminopolycarboxylic acids.
format Article
author Trunova , Elena
Mishchenko , Artem
Makotryk , Tamara
spellingShingle Trunova , Elena
Mishchenko , Artem
Makotryk , Tamara
CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ
author_facet Trunova , Elena
Mishchenko , Artem
Makotryk , Tamara
author_sort Trunova , Elena
title CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ
title_short CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ
title_full CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ
title_fullStr CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ
title_full_unstemmed CИНТЕЗ ТА СПЕКТРАЛЬНІ ХАРАКТЕРИСТИКИ ГЕТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ Pr(IІI) іЗ Zn(II), Со(ІІ) НА ОСНОВІ ЕТИЛЕНДИАМІНТЕТРАОЦТОВОЇ ТА ЕТИЛЕНДИАМІНДИЯНТАРНОЇ КИСЛОТ
title_sort cинтез та спектральні характеристики гетерометалічних комплексів pr(iіi) із zn(ii), со(іі) на основі етилендиамінтетраоцтової та етилендиаміндиянтарної кислот
title_alt SYNTHESIS AND SPECTRAL CHARACTERISTICS OF HETEROMETALLIC COMPLEXES OF Pr(III) WITH Zn(II), CO(II) BASED ON ETHYLENEDIAMINETETRAACETIC AND ETHYLENEDIAMINEDISUCCINIC ACIDS
description New heterometallic f-d-complexes of Pr (III), Co(II), Zn(II) with aminopolycarboxylic acids (ethylenediaminetetraacetic, ethylenediaminedisuccinic acids) have been synthesized and spectroscopically characterized. It was found that complexes with a molar ratio of Pr:M3d: EDTA=1:2:2 are formed for ethylenediaminetetraacetic compounds, and that in the case of complexes based on EDDS, heteronuclear compounds of the equimolar composition Pr: M3d: EDDS = 1: 1: 1 are formed. It is shown that it is expedient to carry out the synthesis of heterometallic complexes on the basis of mono­nuclear polycarboxylates of 3d metals, which act as a «building block» for the preparation of a heterobinuclear compound by the exo coordination of additional metal ions. The complexes are characterized by the method of electron absorption spectroscopy. It is shown that independent of 3d-metal, for both heterometallic systems based on EDDS, a hypsochromic shift of the absorption maxima relative to νmax is observed for the homonuclear praseodymium complex. For ethylenediaminetetraacetate systems, the absorption maxima undergo both low- and high-frequency shift, which indicates the different nature of the ligand field effect, which is caused primarily by differences in the structure of the corresponding heteronuclearaminopolycarboxylates due to the presence of a chiral carbon atom in the EDDS molecule. For the supersensitive transitions Pr(III)) 3H4 →3P2 and 3H4 → 1D2 , the covalence parameters of the Ln-O bond have been calculated: osci­llator power (P), nepheloxetic parameter (β), covalence parameter (b1/2), Sinha parameter (δ). Analysis of the spectroscopic parameters indicates a decrease in the covalence of the lanthanide-ligand bond in the transition from mono- to heteronuclear complex, and a decrease in the local symmetry of the lanthanide ion occurs in the order Ln (III) aqua ion <hete­rometallic complex <monometallic complex. Heteronuclear complexes are several orders of magnitude more stable than mononuclear ones due to the formation of additional bonds or metallacycles with donor ligand atoms. It is noted that the stability of complexes with EDDS is lower than that of the corresponding complexes with EDTA due to the different size and number of chelated metallacycles. The obtained heteronuclear complexes belong to folded complexes, in which the ligand-complexone realizes the maximum denticity to the lanthanide ion, and the coordination sphere of the 3d-cation is formed by carboxyl groups EDTA / EDDS and inner-sphere water molecules. In this case, the ions of 3d-metals are in a distorted octahedral environment, and the coordination number of Pr(III) is 8.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2021
url https://ucj.org.ua/index.php/journal/article/view/286
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