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Ferrocenophanium Stability and Catalysis

Ferrocenium catalysis is a vibrant research area, and an increasing number of ferrocenium-catalyzed processes have been reported in the recent years. However, the ferrocenium cation is not very stable in solution, which may potentially hamper catalytic applications. In an effort to stabilize ferroce...

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Autores principales: Bezawada, Sai Anvesh, Ušto, Neira, Wilke, Chloe, Barnes-Flaspoler, Michael, Jagan, Rajamoni, Bauer, Eike B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10058812/
https://www.ncbi.nlm.nih.gov/pubmed/36985702
http://dx.doi.org/10.3390/molecules28062729
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author Bezawada, Sai Anvesh
Ušto, Neira
Wilke, Chloe
Barnes-Flaspoler, Michael
Jagan, Rajamoni
Bauer, Eike B.
author_facet Bezawada, Sai Anvesh
Ušto, Neira
Wilke, Chloe
Barnes-Flaspoler, Michael
Jagan, Rajamoni
Bauer, Eike B.
author_sort Bezawada, Sai Anvesh
collection PubMed
description Ferrocenium catalysis is a vibrant research area, and an increasing number of ferrocenium-catalyzed processes have been reported in the recent years. However, the ferrocenium cation is not very stable in solution, which may potentially hamper catalytic applications. In an effort to stabilize ferrocenium-type architectures by inserting a bridge between the cyclopentadienyl rings, we investigated two ferrocenophanium (or ansa-ferrocenium) cations with respect to their stability and catalytic activity in propargylic substitution reactions. One of the ferrocenophanium complexes was characterized by single crystal X-ray diffraction. Cyclic voltammetry experiments of the ferrocenophane parent compounds were performed in the absence and presence of alcohol nucleophiles, and the stability of the cations in solution was judged based on the reversibility of the electron transfer. The experiments revealed a moderate stabilizing effect of the bridge, albeit the effect is not very pronounced or straightforward. Catalytic propargylic substitution test reactions revealed decreased activity of the ferrocenophanium cations compared to the ferrocenium cation. It appears that the somewhat stabilized ferrocenophanium cations show decreased catalytic activity.
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spelling pubmed-100588122023-03-30 Ferrocenophanium Stability and Catalysis Bezawada, Sai Anvesh Ušto, Neira Wilke, Chloe Barnes-Flaspoler, Michael Jagan, Rajamoni Bauer, Eike B. Molecules Article Ferrocenium catalysis is a vibrant research area, and an increasing number of ferrocenium-catalyzed processes have been reported in the recent years. However, the ferrocenium cation is not very stable in solution, which may potentially hamper catalytic applications. In an effort to stabilize ferrocenium-type architectures by inserting a bridge between the cyclopentadienyl rings, we investigated two ferrocenophanium (or ansa-ferrocenium) cations with respect to their stability and catalytic activity in propargylic substitution reactions. One of the ferrocenophanium complexes was characterized by single crystal X-ray diffraction. Cyclic voltammetry experiments of the ferrocenophane parent compounds were performed in the absence and presence of alcohol nucleophiles, and the stability of the cations in solution was judged based on the reversibility of the electron transfer. The experiments revealed a moderate stabilizing effect of the bridge, albeit the effect is not very pronounced or straightforward. Catalytic propargylic substitution test reactions revealed decreased activity of the ferrocenophanium cations compared to the ferrocenium cation. It appears that the somewhat stabilized ferrocenophanium cations show decreased catalytic activity. MDPI 2023-03-17 /pmc/articles/PMC10058812/ /pubmed/36985702 http://dx.doi.org/10.3390/molecules28062729 Text en © 2023 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
Bezawada, Sai Anvesh
Ušto, Neira
Wilke, Chloe
Barnes-Flaspoler, Michael
Jagan, Rajamoni
Bauer, Eike B.
Ferrocenophanium Stability and Catalysis
title Ferrocenophanium Stability and Catalysis
title_full Ferrocenophanium Stability and Catalysis
title_fullStr Ferrocenophanium Stability and Catalysis
title_full_unstemmed Ferrocenophanium Stability and Catalysis
title_short Ferrocenophanium Stability and Catalysis
title_sort ferrocenophanium stability and catalysis
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10058812/
https://www.ncbi.nlm.nih.gov/pubmed/36985702
http://dx.doi.org/10.3390/molecules28062729
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