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  Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol

Gennari, M., Brazzolotto, D., Pécaut, J., Cherrier, M. V., Pollock, C. J., DeBeer, S., et al. (2015). Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol. Journal of the American Chemical Society, 137(26), 8644-8653. doi:10.1021/jacs.5b04917.

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Gennari, Marcello1, Author
Brazzolotto, Deborah1, Author
Pécaut, Jacques2, 3, Author
Cherrier, Mickael V.4, 5, 6, 7, Author
Pollock, Chistopher J.8, Author           
DeBeer, Serena8, 9, Author           
Retegan, Marius8, Author           
Pantazis, Dimitrios A.8, Author           
Neese, Frank8, Author           
Rouzières, Mathieu10, 11, Author
Clérac, Rodolphe10, 11, Author
Duboc, Carole1, Author
1CNRS UMR 5250, DCM, Université Grenoble Alpes, F-38000 Grenoble, France, ou_persistent22              
2INAC-SCIB, Université Grenoble Alpes, F-38000 Grenoble, France, ou_persistent22              
3Reconnaissance Ionique et Chimie de Coordination, CEA, INAC-SCIB, F-38000 Grenoble, France, ou_persistent22              
4Metalloproteins Unit, Institut de Biologie Structurale Jean-Pierre Ebel, CEA, CNRS UMR 5075, Université Grenoble Alpes, 41 rue Horowitz, 38027 Grenoble Cedex 1, France, ou_persistent22              
5Université de Lyon, F-69622 Lyon, France, ou_persistent22              
6Université Claude Bernard Lyon 1, F-69622 Villeurbanne, France, ou_persistent22              
7CNRS, UMR 5086 Bases Moléculaires et Structurales de Systèmes Infectieux, Institut de Biologie et Chimie des Protéines, 7 Passage du Vercors, F-69367 Lyon, France, ou_persistent22              
8Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
9Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States, ou_persistent22              
10CNRS, CRPP, UPR 8641, F-33600 Pessac, France, ou_persistent22              
11CRPP, UPR 8641, Université Bordeaux, F-33600 Pessac, France, ou_persistent22              


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 Abstract: Herein, we describe an uncommon example of a manganese–thiolate complex, which is capable of activating dioxygen and catalyzing its two-electron reduction to generate H2O2. The structurally characterized dimercapto-bridged MnII dimer [MnII2(LS)(LSH)]ClO4 (MnII2SH) is formed by reaction of the LS ligand (2,2′-(2,2′-bipyridine-6,6′-diyl)bis(1,1-diphenylethanethiolate)) with MnII. The unusual presence of a pendant thiol group bound to one MnII ion in MnII2SH is evidenced both in the solid state and in solution. The MnII2SH complex reacts with dioxygen in CH3CN, leading to the formation of a rare mono-μ-hydroxo dinuclear MnIII complex, [(MnIII2(LS)2(OH)]ClO4 (MnIII2OH), which has also been structurally characterized. When MnII2SH reacts with O2 in the presence of a proton source, 2,6-lutidinium tetrafluoroborate (up to 50 equiv), the formation of a new Mn species is observed, assigned to a bis-μ-thiolato dinuclear MnIII complex with two terminal thiolate groups (MnIII2), with the concomitant production of H2O2 up to ∼40% vs MnII2SH. The addition of a catalytic amount of MnII2SH to an air-saturated solution of MenFc (n = 8 or 10) and 2,6-lutidinium tetrafluoroborate results in the quantitative and efficient oxidation of MenFc by O2 to afford the respective ferrocenium derivatives (MenFc+, with n = 8 or 10). Hydrogen peroxide is mainly produced during the catalytic reduction of dioxygen with 80–84% selectivity, making the MnII2SH complex a rare Mn-based active catalyst for two-electron O2 reduction.


Language(s): eng - English
 Dates: 2015-05-122015-06-292015-07-08
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.5b04917
 Degree: -



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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 137 (26) Sequence Number: - Start / End Page: 8644 - 8653 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870