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Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes
The complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH(3))(OH)(2)) and hemiacetal (RCH(OH)(...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9033980/ https://www.ncbi.nlm.nih.gov/pubmed/35479880 http://dx.doi.org/10.1039/d1ra02512k |
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author | Crespi, Ayelén F. Sánchez, Verónica M. Vega, Daniel Pérez, Ana L. Brondino, Carlos D. Linck, Yamila Garro Hodgkinson, Paul Rodríguez-Castellón, Enrique Lázaro-Martínez, Juan M. |
author_facet | Crespi, Ayelén F. Sánchez, Verónica M. Vega, Daniel Pérez, Ana L. Brondino, Carlos D. Linck, Yamila Garro Hodgkinson, Paul Rodríguez-Castellón, Enrique Lázaro-Martínez, Juan M. |
author_sort | Crespi, Ayelén F. |
collection | PubMed |
description | The complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH(3))(OH)(2)) and hemiacetal (RCH(OH)(OCH(3))) moieties in both 4-pyridinecarboxaldehyde copper and cobalt complexes. In contrast, the aldehyde group is retained when the 3-pyridinecarboxaldehyde ligand is complexed with cobalt. In the different copper complexes, similar paramagnetic (1)H resonance lines were obtained in the solid state; however, the connectivity with the carbon structure and the (1)H vicinities were done with 2D (1)H–(13)C HETCOR, (1)H–(1)H SQ/DQ and proton spin diffusion (PSD) experiments. The strong paramagnetic effect exerted by the cobalt center prevented the observation of (13)C NMR signals and chemical information could only be obtained from X-ray experiments. 2D PSD experiments in the solid state were useful for the proton assignments in both Cu(ii) complexes. The combination of X-ray crystallography experiments with DFT calculations together with the experimental results obtained from EPR and solid-state NMR allowed the assignment of NMR signals in pyridinecarboxaldehyde ligands coordinated with copper ions. In cases where the crystallographic information was not available, as in the case of the 3-pyridinecarboxaldehyde Cu(ii) complex, the combination of these techniques allowed not only the assignment of NMR signals but also the study of the functionalization of the substituent group. |
format | Online Article Text |
id | pubmed-9033980 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-90339802022-04-26 Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes Crespi, Ayelén F. Sánchez, Verónica M. Vega, Daniel Pérez, Ana L. Brondino, Carlos D. Linck, Yamila Garro Hodgkinson, Paul Rodríguez-Castellón, Enrique Lázaro-Martínez, Juan M. RSC Adv Chemistry The complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH(3))(OH)(2)) and hemiacetal (RCH(OH)(OCH(3))) moieties in both 4-pyridinecarboxaldehyde copper and cobalt complexes. In contrast, the aldehyde group is retained when the 3-pyridinecarboxaldehyde ligand is complexed with cobalt. In the different copper complexes, similar paramagnetic (1)H resonance lines were obtained in the solid state; however, the connectivity with the carbon structure and the (1)H vicinities were done with 2D (1)H–(13)C HETCOR, (1)H–(1)H SQ/DQ and proton spin diffusion (PSD) experiments. The strong paramagnetic effect exerted by the cobalt center prevented the observation of (13)C NMR signals and chemical information could only be obtained from X-ray experiments. 2D PSD experiments in the solid state were useful for the proton assignments in both Cu(ii) complexes. The combination of X-ray crystallography experiments with DFT calculations together with the experimental results obtained from EPR and solid-state NMR allowed the assignment of NMR signals in pyridinecarboxaldehyde ligands coordinated with copper ions. In cases where the crystallographic information was not available, as in the case of the 3-pyridinecarboxaldehyde Cu(ii) complex, the combination of these techniques allowed not only the assignment of NMR signals but also the study of the functionalization of the substituent group. The Royal Society of Chemistry 2021-06-09 /pmc/articles/PMC9033980/ /pubmed/35479880 http://dx.doi.org/10.1039/d1ra02512k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Crespi, Ayelén F. Sánchez, Verónica M. Vega, Daniel Pérez, Ana L. Brondino, Carlos D. Linck, Yamila Garro Hodgkinson, Paul Rodríguez-Castellón, Enrique Lázaro-Martínez, Juan M. Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes |
title | Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes |
title_full | Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes |
title_fullStr | Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes |
title_full_unstemmed | Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes |
title_short | Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes |
title_sort | paramagnetic solid-state nmr assignment and novel chemical conversion of the aldehyde group to dihydrogen ortho ester and hemiacetal moieties in copper(ii)- and cobalt(ii)-pyridinecarboxaldehyde complexes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9033980/ https://www.ncbi.nlm.nih.gov/pubmed/35479880 http://dx.doi.org/10.1039/d1ra02512k |
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