Cargando…
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...
Autores principales: | , , , , , , , |
---|---|
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 |
_version_ | 1784666947853484032 |
---|---|
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. |
format | Online Article Text |
id | pubmed-8911866 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT routzomanianastasia confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants AT ladazoig confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants AT angelidouvarvara confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants AT praptopouloucatherine confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants AT psycharisvassilis confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants AT konidariskonstantisf confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants AT chasapischristost confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants AT perlepesspyrosp confirmingthemolecularbasisofthesolventextractionofcadmiumiiusing2pyridyloximesthroughasyntheticinorganicchemistryapproachandaproposalformoreefficientextractants |