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Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction
A family of bis[(R or S)‐N‐1‐(Ar)ethylsalicylaldiminato‐κ(2)N,O]‐Δ/Λ‐zinc(II) {Ar=C(6)H(5) (ZnRL(1) or ZnSL(1)), p‐CH(3)OC(6)H(4) (ZnRL(2) or ZnSL(2)) and p‐ClC(6)H(4) (ZnRL(3) or ZnSL(3))} compounds was synthesized and investigated by multiple methods. They feature Λ/Δ‐chirality‐at‐metal induction...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9278105/ https://www.ncbi.nlm.nih.gov/pubmed/35822916 http://dx.doi.org/10.1002/open.202200116 |
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author | Enamullah, Mohammed Mostafizur Rahman, Mohammad Khairul Islam, Mohammad Woschko, Dennis Janiak, Christoph Pescitelli, Gennaro |
author_facet | Enamullah, Mohammed Mostafizur Rahman, Mohammad Khairul Islam, Mohammad Woschko, Dennis Janiak, Christoph Pescitelli, Gennaro |
author_sort | Enamullah, Mohammed |
collection | PubMed |
description | A family of bis[(R or S)‐N‐1‐(Ar)ethylsalicylaldiminato‐κ(2)N,O]‐Δ/Λ‐zinc(II) {Ar=C(6)H(5) (ZnRL(1) or ZnSL(1)), p‐CH(3)OC(6)H(4) (ZnRL(2) or ZnSL(2)) and p‐ClC(6)H(4) (ZnRL(3) or ZnSL(3))} compounds was synthesized and investigated by multiple methods. They feature Λ/Δ‐chirality‐at‐metal induction along the pseudo‐C (2) axis of the molecules. The chirality induction is quantitative in the solid state, explored by X‐ray crystallography and powder X‐ray diffraction (PXRD), where R or S‐ligated complexes diastereoselectively yield Λ or Δ‐configuration at the metal. On the other hand, Λ and Δ‐diastereomers co‐exist in solution. The Λ⇆Δ equilibrium is solvent‐ and temperature‐dependent. Electronic circular dichroism (ECD) spectra confirm the existence of a diastereomeric excess of Λ‐ZnRL(1−3) or Δ‐ZnSL(1−3) in solution. DSC analysis reveals thermally induced irreversible phase transformation from a crystalline solid to an isotropic liquid phase. ECD spectra were reproduced by DFT geometry optimizations and time‐dependent DFT (TD‐DFT) calculations, providing ultimate proof of the dominant chirality atmetal in solution. |
format | Online Article Text |
id | pubmed-9278105 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-92781052022-07-15 Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction Enamullah, Mohammed Mostafizur Rahman, Mohammad Khairul Islam, Mohammad Woschko, Dennis Janiak, Christoph Pescitelli, Gennaro ChemistryOpen Research Articles A family of bis[(R or S)‐N‐1‐(Ar)ethylsalicylaldiminato‐κ(2)N,O]‐Δ/Λ‐zinc(II) {Ar=C(6)H(5) (ZnRL(1) or ZnSL(1)), p‐CH(3)OC(6)H(4) (ZnRL(2) or ZnSL(2)) and p‐ClC(6)H(4) (ZnRL(3) or ZnSL(3))} compounds was synthesized and investigated by multiple methods. They feature Λ/Δ‐chirality‐at‐metal induction along the pseudo‐C (2) axis of the molecules. The chirality induction is quantitative in the solid state, explored by X‐ray crystallography and powder X‐ray diffraction (PXRD), where R or S‐ligated complexes diastereoselectively yield Λ or Δ‐configuration at the metal. On the other hand, Λ and Δ‐diastereomers co‐exist in solution. The Λ⇆Δ equilibrium is solvent‐ and temperature‐dependent. Electronic circular dichroism (ECD) spectra confirm the existence of a diastereomeric excess of Λ‐ZnRL(1−3) or Δ‐ZnSL(1−3) in solution. DSC analysis reveals thermally induced irreversible phase transformation from a crystalline solid to an isotropic liquid phase. ECD spectra were reproduced by DFT geometry optimizations and time‐dependent DFT (TD‐DFT) calculations, providing ultimate proof of the dominant chirality atmetal in solution. John Wiley and Sons Inc. 2022-07-13 /pmc/articles/PMC9278105/ /pubmed/35822916 http://dx.doi.org/10.1002/open.202200116 Text en © 2022 The Authors. Published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Research Articles Enamullah, Mohammed Mostafizur Rahman, Mohammad Khairul Islam, Mohammad Woschko, Dennis Janiak, Christoph Pescitelli, Gennaro Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction |
title | Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction |
title_full | Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction |
title_fullStr | Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction |
title_full_unstemmed | Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction |
title_short | Characterization of Diastereomeric Equilibria of Pseudotetrahedral Bis[(R or S)‐N‐1‐(Ar)Ethylsalicylaldiminato‐κ(2)N,O]zinc(II) with Λ/Δ‐Chirality‐At‐Metal Induction |
title_sort | characterization of diastereomeric equilibria of pseudotetrahedral bis[(r or s)‐n‐1‐(ar)ethylsalicylaldiminato‐κ(2)n,o]zinc(ii) with λ/δ‐chirality‐at‐metal induction |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9278105/ https://www.ncbi.nlm.nih.gov/pubmed/35822916 http://dx.doi.org/10.1002/open.202200116 |
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