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

Abstract

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)FeIII–OH2 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, University of Wisconsin-Madison, Madison, USA
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1531026
Alternate Identifier(s):
OSTI ID: 1609612
Grant/Contract Number:  
FG02-05ER15690; CHE-1305124; DGE-1747503; CHE-1048642
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 32; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Das, Amit, Nutting, Jordan E., and Stahl, Shannon S. Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source. United Kingdom: N. p., 2019. Web. doi:10.1039/C9SC02609F.
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. United Kingdom. doi:10.1039/C9SC02609F.
Das, Amit, Nutting, Jordan E., and Stahl, Shannon S. Wed . "Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source". United Kingdom. doi:10.1039/C9SC02609F.
@article{osti_1531026,
title = {Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source},
author = {Das, Amit and Nutting, Jordan E. and Stahl, Shannon S.},
abstractNote = {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)FeIII–OH2 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.},
doi = {10.1039/C9SC02609F},
journal = {Chemical Science},
number = 32,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9SC02609F

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Cited by: 6 works
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