Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source

High-valent iron-oxo complexes are key intermediates in C–H functionalization reactions. Herein, we report the generation of a (TAML)Fe-oxo species (TAML = tetraamido macrocyclic ligand) via electrochemical proton-coupled oxidation of the corresponding (TAML)Fe(III)–OH(2) complex. Cyclic voltammetry...

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Detalles Bibliográficos
Autores principales: Das, Amit, Nutting, Jordan E., Stahl, Shannon S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2019
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6761876/
https://www.ncbi.nlm.nih.gov/pubmed/31588305
http://dx.doi.org/10.1039/c9sc02609f
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author Das, Amit
Nutting, Jordan E.
Stahl, Shannon S.
author_facet Das, Amit
Nutting, Jordan E.
Stahl, Shannon S.
author_sort Das, Amit
collection PubMed
description High-valent iron-oxo complexes are key intermediates in C–H functionalization reactions. Herein, we report the generation of a (TAML)Fe-oxo species (TAML = tetraamido macrocyclic ligand) via electrochemical proton-coupled oxidation of the corresponding (TAML)Fe(III)–OH(2) complex. Cyclic voltammetry (CV) and spectroelectrochemical studies are used to elucidate the relevant (TAML)Fe redox processes and determine the predominant (TAML)Fe species present in solution during bulk electrolysis. Evidence for iron(iv) and iron(v) species is presented, and these species are used in the electrochemical oxygenation of benzylic C–H bonds and dehydrogenation of alcohols to ketones.
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spelling pubmed-67618762019-10-04 Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source Das, Amit Nutting, Jordan E. Stahl, Shannon S. Chem Sci Chemistry High-valent iron-oxo complexes are key intermediates in C–H functionalization reactions. Herein, we report the generation of a (TAML)Fe-oxo species (TAML = tetraamido macrocyclic ligand) via electrochemical proton-coupled oxidation of the corresponding (TAML)Fe(III)–OH(2) complex. Cyclic voltammetry (CV) and spectroelectrochemical studies are used to elucidate the relevant (TAML)Fe redox processes and determine the predominant (TAML)Fe species present in solution during bulk electrolysis. Evidence for iron(iv) and iron(v) species is presented, and these species are used in the electrochemical oxygenation of benzylic C–H bonds and dehydrogenation of alcohols to ketones. Royal Society of Chemistry 2019-06-27 /pmc/articles/PMC6761876/ /pubmed/31588305 http://dx.doi.org/10.1039/c9sc02609f Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Das, Amit
Nutting, Jordan E.
Stahl, Shannon S.
Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source
title Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source
title_full Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source
title_fullStr Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source
title_full_unstemmed Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source
title_short Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source
title_sort electrochemical c–h oxygenation and alcohol dehydrogenation involving fe-oxo species using water as the oxygen source
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6761876/
https://www.ncbi.nlm.nih.gov/pubmed/31588305
http://dx.doi.org/10.1039/c9sc02609f
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AT stahlshannons electrochemicalchoxygenationandalcoholdehydrogenationinvolvingfeoxospeciesusingwaterastheoxygensource

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