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Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation

Two pentadentate ligands built on the 2-aminomethylpiperidine structure and bearing two tertiary amino and three oxygen donors (three carboxylates in the case of AMPTA and two carboxylates and one phenolate for AMPDA-HB) were developed for Mn(II) complexation. Equilibrium studies on the ligands and...

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Autores principales: Martinelli, Jonathan, Callegari, Edoardo, Baranyai, Zsolt, Fraccarollo, Alberto, Cossi, Maurizio, Tei, Lorenzo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8513077/
https://www.ncbi.nlm.nih.gov/pubmed/34641536
http://dx.doi.org/10.3390/molecules26195993
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author Martinelli, Jonathan
Callegari, Edoardo
Baranyai, Zsolt
Fraccarollo, Alberto
Cossi, Maurizio
Tei, Lorenzo
author_facet Martinelli, Jonathan
Callegari, Edoardo
Baranyai, Zsolt
Fraccarollo, Alberto
Cossi, Maurizio
Tei, Lorenzo
author_sort Martinelli, Jonathan
collection PubMed
description Two pentadentate ligands built on the 2-aminomethylpiperidine structure and bearing two tertiary amino and three oxygen donors (three carboxylates in the case of AMPTA and two carboxylates and one phenolate for AMPDA-HB) were developed for Mn(II) complexation. Equilibrium studies on the ligands and the Mn(II) complexes were carried out using pH potentiometry, (1)H-NMR spectroscopy and UV-vis spectrophotometry. The Mn complexes that were formed by the two ligands were more stable than the Mn complexes of other pentadentate ligands but with a lower pMn than Mn(EDTA) and Mn(CDTA) (pMn for Mn(AMPTA) = 7.89 and for Mn(AMPDA-HB) = 7.07). (1)H and (17)O-NMR relaxometric studies showed that the two Mn-complexes were q = 1 with a relaxivity value of 3.3 mM(−1) s(−1) for Mn(AMPTA) and 3.4 mM(−1) s(−1) for Mn(AMPDA-HB) at 20 MHz and 298 K. Finally, the geometries of the two complexes were optimized at the DFT level, finding an octahedral coordination environment around the Mn(2+) ion, and MD simulations were performed to monitor the distance between the Mn(2+) ion and the oxygen of the coordinated water molecule to estimate its residence time, which was in good agreement with that determined using the (17)O NMR data.
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spelling pubmed-85130772021-10-14 Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation Martinelli, Jonathan Callegari, Edoardo Baranyai, Zsolt Fraccarollo, Alberto Cossi, Maurizio Tei, Lorenzo Molecules Article Two pentadentate ligands built on the 2-aminomethylpiperidine structure and bearing two tertiary amino and three oxygen donors (three carboxylates in the case of AMPTA and two carboxylates and one phenolate for AMPDA-HB) were developed for Mn(II) complexation. Equilibrium studies on the ligands and the Mn(II) complexes were carried out using pH potentiometry, (1)H-NMR spectroscopy and UV-vis spectrophotometry. The Mn complexes that were formed by the two ligands were more stable than the Mn complexes of other pentadentate ligands but with a lower pMn than Mn(EDTA) and Mn(CDTA) (pMn for Mn(AMPTA) = 7.89 and for Mn(AMPDA-HB) = 7.07). (1)H and (17)O-NMR relaxometric studies showed that the two Mn-complexes were q = 1 with a relaxivity value of 3.3 mM(−1) s(−1) for Mn(AMPTA) and 3.4 mM(−1) s(−1) for Mn(AMPDA-HB) at 20 MHz and 298 K. Finally, the geometries of the two complexes were optimized at the DFT level, finding an octahedral coordination environment around the Mn(2+) ion, and MD simulations were performed to monitor the distance between the Mn(2+) ion and the oxygen of the coordinated water molecule to estimate its residence time, which was in good agreement with that determined using the (17)O NMR data. MDPI 2021-10-02 /pmc/articles/PMC8513077/ /pubmed/34641536 http://dx.doi.org/10.3390/molecules26195993 Text en © 2021 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
Martinelli, Jonathan
Callegari, Edoardo
Baranyai, Zsolt
Fraccarollo, Alberto
Cossi, Maurizio
Tei, Lorenzo
Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation
title Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation
title_full Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation
title_fullStr Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation
title_full_unstemmed Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation
title_short Semi-Rigid (Aminomethyl) Piperidine-Based Pentadentate Ligands for Mn(II) Complexation
title_sort semi-rigid (aminomethyl) piperidine-based pentadentate ligands for mn(ii) complexation
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8513077/
https://www.ncbi.nlm.nih.gov/pubmed/34641536
http://dx.doi.org/10.3390/molecules26195993
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