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Modulating alkene reactivity from oxygenation to halogenation via electrochemical O2 activation by Mn porphyrin

Authors :
Elodie Anxolabéhère-Mallart
Claire Fave
Frédéric Banse
Nikolaos Kostopoulos
Laboratoire d'Electrochimie Moléculaire (LEM (UMR_7591))
Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)
Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO)
Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Source :
Chemical Communications, Chemical Communications, Royal Society of Chemistry, 2021, 57 (10), pp.1198-1201. ⟨10.1039/d0cc07531k⟩
Publication Year :
2021
Publisher :
Royal Society of Chemistry (RSC), 2021.

Abstract

International audience; Oxidation of organic substrates is achieved in nature under mild conditions thanks to metalloenzymes but remains a challenge for chemists. Herein we show by UV-Vis spectroelectrochemistry that when MnIIITPPCl is electrochemically reduced to MnII in CH2Cl2 under O2, a MnIIO2˙ species is generated. Benzoic anhydride reacts with the latter triggering a catalytic current in cyclic voltammetry. Electrolysis on the catalytic wave in the presence of cyclooctene leads to its oxygenation or halogenation depending on the axial ligand present as reported here for the first time.

Details

ISSN :
1364548X and 13597345
Volume :
57
Database :
OpenAIRE
Journal :
Chemical Communications
Accession number :
edsair.doi.dedup.....d18f5c633c9be555ce8a66aea90309ec