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Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents

In this work, the syntheses of non‐coordinated electron‐rich phenolate anions via deprotonation of the corresponding alcohols with an extremely powerful perethyl tetraphosphazene base (Schwesinger base) are reported. The application of uncharged phosphazenes renders the selective preparation of anio...

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Autores principales: Weitkamp, Robin F., Neumann, Beate, Stammler, Hans‐Georg, Hoge, Berthold
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8247865/
https://www.ncbi.nlm.nih.gov/pubmed/33368714
http://dx.doi.org/10.1002/chem.202005123
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author Weitkamp, Robin F.
Neumann, Beate
Stammler, Hans‐Georg
Hoge, Berthold
author_facet Weitkamp, Robin F.
Neumann, Beate
Stammler, Hans‐Georg
Hoge, Berthold
author_sort Weitkamp, Robin F.
collection PubMed
description In this work, the syntheses of non‐coordinated electron‐rich phenolate anions via deprotonation of the corresponding alcohols with an extremely powerful perethyl tetraphosphazene base (Schwesinger base) are reported. The application of uncharged phosphazenes renders the selective preparation of anionic phenol‐phenolate and phenolate hydrates possible, which allows for the investigation of hydrogen bonding in these species. Hydrogen bonding brings about decreased redox potentials relative to the corresponding non‐coordinated phenolate anions. The latter show redox potentials of up to −0.72(1) V vs. SCE, which is comparable to that of zinc metal, thus qualifying their application as organic zinc mimics. We utilized phenolates as reducing agents for the generation of radical anions in addition to the corresponding phenoxyl radicals. A tetracyanoethylene radical anion salt was synthesized and fully characterized as a representative example. We also present the activation of sulfur hexafluoride (SF(6)) with phenolates in a SET reaction, in which the nature of the respective phenolate determines whether simple fluorides or pentafluorosulfanide ([SF(5)](−)) salts are formed.
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spelling pubmed-82478652021-07-02 Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents Weitkamp, Robin F. Neumann, Beate Stammler, Hans‐Georg Hoge, Berthold Chemistry Full Papers In this work, the syntheses of non‐coordinated electron‐rich phenolate anions via deprotonation of the corresponding alcohols with an extremely powerful perethyl tetraphosphazene base (Schwesinger base) are reported. The application of uncharged phosphazenes renders the selective preparation of anionic phenol‐phenolate and phenolate hydrates possible, which allows for the investigation of hydrogen bonding in these species. Hydrogen bonding brings about decreased redox potentials relative to the corresponding non‐coordinated phenolate anions. The latter show redox potentials of up to −0.72(1) V vs. SCE, which is comparable to that of zinc metal, thus qualifying their application as organic zinc mimics. We utilized phenolates as reducing agents for the generation of radical anions in addition to the corresponding phenoxyl radicals. A tetracyanoethylene radical anion salt was synthesized and fully characterized as a representative example. We also present the activation of sulfur hexafluoride (SF(6)) with phenolates in a SET reaction, in which the nature of the respective phenolate determines whether simple fluorides or pentafluorosulfanide ([SF(5)](−)) salts are formed. John Wiley and Sons Inc. 2021-02-08 2021-04-12 /pmc/articles/PMC8247865/ /pubmed/33368714 http://dx.doi.org/10.1002/chem.202005123 Text en © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Weitkamp, Robin F.
Neumann, Beate
Stammler, Hans‐Georg
Hoge, Berthold
Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents
title Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents
title_full Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents
title_fullStr Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents
title_full_unstemmed Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents
title_short Non‐coordinated and Hydrogen Bonded Phenolate Anions as One‐Electron Reducing Agents
title_sort non‐coordinated and hydrogen bonded phenolate anions as one‐electron reducing agents
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8247865/
https://www.ncbi.nlm.nih.gov/pubmed/33368714
http://dx.doi.org/10.1002/chem.202005123
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