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Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference
The weak noncovalent interactions and flexibility of ligands play a key role in enantioselective metal‐catalyzed reactions. In transition metal complexes and their catalytic applications, the experimental assessment and the design of key interactions is as difficult as the prediction of the enantios...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9298319/ https://www.ncbi.nlm.nih.gov/pubmed/34585835 http://dx.doi.org/10.1002/anie.202106881 |
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author | Žabka, Matej Naviri, Lavakumar Gschwind, Ruth M. |
author_facet | Žabka, Matej Naviri, Lavakumar Gschwind, Ruth M. |
author_sort | Žabka, Matej |
collection | PubMed |
description | The weak noncovalent interactions and flexibility of ligands play a key role in enantioselective metal‐catalyzed reactions. In transition metal complexes and their catalytic applications, the experimental assessment and the design of key interactions is as difficult as the prediction of the enantioselectivities, especially for flexible, privileged ligands such as chiral phosphoramidites. Therefore, the interligand interactions in cis‐Pd(II)L(2)Cl(2) phosphoramidite complexes were investigated by NMR spectroscopy and computations. We were able to induce a strong conformational preference by breaking the symmetry of the C(2)‐symmetric side chain of one of the ligands, and shift the equilibrium between hetero‐ and homocomplexes towards heterocomplexes because of interligand interactions in the cis‐complexes. The modulation of aryl substituents was exploited, along with the solvent effect. The combined CH–π and π–π interactions reveal design patterns for binding and folding of chiral ligands and catalysts. |
format | Online Article Text |
id | pubmed-9298319 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-92983192022-07-21 Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference Žabka, Matej Naviri, Lavakumar Gschwind, Ruth M. Angew Chem Int Ed Engl Research Articles The weak noncovalent interactions and flexibility of ligands play a key role in enantioselective metal‐catalyzed reactions. In transition metal complexes and their catalytic applications, the experimental assessment and the design of key interactions is as difficult as the prediction of the enantioselectivities, especially for flexible, privileged ligands such as chiral phosphoramidites. Therefore, the interligand interactions in cis‐Pd(II)L(2)Cl(2) phosphoramidite complexes were investigated by NMR spectroscopy and computations. We were able to induce a strong conformational preference by breaking the symmetry of the C(2)‐symmetric side chain of one of the ligands, and shift the equilibrium between hetero‐ and homocomplexes towards heterocomplexes because of interligand interactions in the cis‐complexes. The modulation of aryl substituents was exploited, along with the solvent effect. The combined CH–π and π–π interactions reveal design patterns for binding and folding of chiral ligands and catalysts. John Wiley and Sons Inc. 2021-11-03 2021-12-01 /pmc/articles/PMC9298319/ /pubmed/34585835 http://dx.doi.org/10.1002/anie.202106881 Text en © 2021 The Authors. Angewandte Chemie International Edition 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 Žabka, Matej Naviri, Lavakumar Gschwind, Ruth M. Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference |
title | Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference |
title_full | Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference |
title_fullStr | Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference |
title_full_unstemmed | Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference |
title_short | Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference |
title_sort | noncovalent ch–π and π–π interactions in phosphoramidite palladium(ii) complexes with strong conformational preference |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9298319/ https://www.ncbi.nlm.nih.gov/pubmed/34585835 http://dx.doi.org/10.1002/anie.202106881 |
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