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Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants

The present work describes the reactions of CdI(2) with 2-pyridyl aldoxime (2paoH), 3-pyridyl aldoxime (3paoH), 4-pyridyl aldoxime (4paoH), 2-6-diacetylpyridine dioxime (dapdoH(2)) and 2,6-pyridyl diamidoxime (LH(4)). The primary goal was to contribute to understanding the molecular basis of the ver...

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Autores principales: Routzomani, Anastasia, Lada, Zoi G., Angelidou, Varvara, P. Raptopoulou, Catherine, Psycharis, Vassilis, Konidaris, Konstantis F., Chasapis, Christos T., Perlepes, Spyros P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8911866/
https://www.ncbi.nlm.nih.gov/pubmed/35268720
http://dx.doi.org/10.3390/molecules27051619
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author Routzomani, Anastasia
Lada, Zoi G.
Angelidou, Varvara
P. Raptopoulou, Catherine
Psycharis, Vassilis
Konidaris, Konstantis F.
Chasapis, Christos T.
Perlepes, Spyros P.
author_facet Routzomani, Anastasia
Lada, Zoi G.
Angelidou, Varvara
P. Raptopoulou, Catherine
Psycharis, Vassilis
Konidaris, Konstantis F.
Chasapis, Christos T.
Perlepes, Spyros P.
author_sort Routzomani, Anastasia
collection PubMed
description The present work describes the reactions of CdI(2) with 2-pyridyl aldoxime (2paoH), 3-pyridyl aldoxime (3paoH), 4-pyridyl aldoxime (4paoH), 2-6-diacetylpyridine dioxime (dapdoH(2)) and 2,6-pyridyl diamidoxime (LH(4)). The primary goal was to contribute to understanding the molecular basis of the very good liquid extraction ability of 2-pyridyl ketoximes with long aliphatic chains towards toxic Cd(II) and the inability of their 4-pyridyl isomers for this extraction. Our systematic investigation provided access to coordination complexes [CdI(2)(2paoH)(2)] (1), {[CdI(2)(3paoH)(2)]}(n) (2), {[CdI(2)(4paoH)(2)]}(n) (3) and [CdI(2)(dapdoH(2))] (4). The reaction of CdI(2) and LH(4) in EtOH resulted in a Cd(II)-involving reaction of the bis(amidoxime) and isolation of [CdI(2)(L’H(2))] (5), where L’H(2) is the new ligand 2,6-bis(ethoxy)pyridine diimine. A mechanism of this transformation has been proposed. The structures of 1, 2, 3, 4·2EtOH and 5 were determined by single-crystal X-ray crystallography. The complexes have been characterized by FT-IR and FT-Raman spectra in the solid state and the data are discussed in terms of structural features. The stability of the complexes in DMSO was investigated by (1)H NMR spectroscopy. Our studies confirm that the excellent extraction ability of 2-pyridyl ketoximes is due to the chelating nature of the extractants leading to thermodynamically stable Cd(II) complexes. The monodentate coordination of 4-pyridyl ketoximes (as confirmed in our model complexes with 4paoH and 3paoH) seems to be responsible for their poor performance as extractants.
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spelling pubmed-89118662022-03-11 Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants Routzomani, Anastasia Lada, Zoi G. Angelidou, Varvara P. Raptopoulou, Catherine Psycharis, Vassilis Konidaris, Konstantis F. Chasapis, Christos T. Perlepes, Spyros P. Molecules Article The present work describes the reactions of CdI(2) with 2-pyridyl aldoxime (2paoH), 3-pyridyl aldoxime (3paoH), 4-pyridyl aldoxime (4paoH), 2-6-diacetylpyridine dioxime (dapdoH(2)) and 2,6-pyridyl diamidoxime (LH(4)). The primary goal was to contribute to understanding the molecular basis of the very good liquid extraction ability of 2-pyridyl ketoximes with long aliphatic chains towards toxic Cd(II) and the inability of their 4-pyridyl isomers for this extraction. Our systematic investigation provided access to coordination complexes [CdI(2)(2paoH)(2)] (1), {[CdI(2)(3paoH)(2)]}(n) (2), {[CdI(2)(4paoH)(2)]}(n) (3) and [CdI(2)(dapdoH(2))] (4). The reaction of CdI(2) and LH(4) in EtOH resulted in a Cd(II)-involving reaction of the bis(amidoxime) and isolation of [CdI(2)(L’H(2))] (5), where L’H(2) is the new ligand 2,6-bis(ethoxy)pyridine diimine. A mechanism of this transformation has been proposed. The structures of 1, 2, 3, 4·2EtOH and 5 were determined by single-crystal X-ray crystallography. The complexes have been characterized by FT-IR and FT-Raman spectra in the solid state and the data are discussed in terms of structural features. The stability of the complexes in DMSO was investigated by (1)H NMR spectroscopy. Our studies confirm that the excellent extraction ability of 2-pyridyl ketoximes is due to the chelating nature of the extractants leading to thermodynamically stable Cd(II) complexes. The monodentate coordination of 4-pyridyl ketoximes (as confirmed in our model complexes with 4paoH and 3paoH) seems to be responsible for their poor performance as extractants. MDPI 2022-02-28 /pmc/articles/PMC8911866/ /pubmed/35268720 http://dx.doi.org/10.3390/molecules27051619 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Routzomani, Anastasia
Lada, Zoi G.
Angelidou, Varvara
P. Raptopoulou, Catherine
Psycharis, Vassilis
Konidaris, Konstantis F.
Chasapis, Christos T.
Perlepes, Spyros P.
Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants
title Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants
title_full Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants
title_fullStr Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants
title_full_unstemmed Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants
title_short Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants
title_sort confirming the molecular basis of the solvent extraction of cadmium(ii) using 2-pyridyl oximes through a synthetic inorganic chemistry approach and a proposal for more efficient extractants
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8911866/
https://www.ncbi.nlm.nih.gov/pubmed/35268720
http://dx.doi.org/10.3390/molecules27051619
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