A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen

Brazzolotto, Deborah; Cantú Reinhard, Fabián G.; Smith‐Jones, Julian; Retegan, Marius; Amidani, Lucia; Faponle, Abayomi S.; Ray, Kallol; Philouze, Christian; de Visser, Sam P.; Gennari, Marcello; Duboc, Carole

doi:10.1002/anie.201703215

Title: A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen

Abstract

Abstract This study deals with the unprecedented reactivity of dinuclear non‐heme Mn ^II –thiolate complexes with O ₂ , which dependent on the protonation state of the initial Mn ^II dimer selectively generates either a di‐μ‐oxo or μ‐oxo‐μ‐hydroxo Mn ^IV complex. Both dimers have been characterized by different techniques including single‐crystal X‐ray diffraction and mass spectrometry. Oxygenation reactions carried out with labeled ¹⁸ O ₂ unambiguously show that the oxygen atoms present in the Mn ^IV dimers originate from O ₂ . Based on experimental observations and DFT calculations, evidence is provided that these Mn ^IV species comproportionate with a Mn ^II precursor to yield μ‐oxo and/or μ‐hydroxo Mn ^III dimers. Our work highlights the delicate balance of reaction conditions to control the synthesis of non‐heme high‐valent μ‐oxo and μ‐hydroxo Mn species from Mn ^II precursors and O ₂ .

Authors:

Brazzolotto, Deborah ^[1];

^[2]; Smith‐Jones, Julian ^[3];

^[4]; Amidani, Lucia ^[4];

^[2]; Ray, Kallol ^[5]; Philouze, Christian ^[3];

^[2]; Gennari, Marcello ^[3];

^[3]

Univ. Grenoble Alpes, CNRS, UMR 5250, DCM 38000 Grenoble France, Univ. Grenoble Alpes, CNRS, UMR 5249, LCBM 38000 Grenoble France
Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science The University of Manchester 131 Princess Street Manchester M1 7DN UK
Univ. Grenoble Alpes, CNRS, UMR 5250, DCM 38000 Grenoble France
European Synchrotron Radiation Facility (ESRF) 71 Avenue des Martyrs 38000 Grenoble France
Department of Chemistry Humboldt-Universität zu Berlin Brook-Taylor-Strasse 2 12489 Berlin Germany

Publication Date:: Fri Jun 09 00:00:00 EDT 2017

Sponsoring Org.:: USDOE

OSTI Identifier:: 1401557

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Angewandte Chemie (International Edition)

Additional Journal Information:: Journal Name: Angewandte Chemie (International Edition) Journal Volume: 56 Journal Issue: 28; Journal ID: ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Citation Formats


                    Brazzolotto, Deborah, Cantú Reinhard, Fabián G., Smith‐Jones, Julian, Retegan, Marius, Amidani, Lucia, Faponle, Abayomi S., Ray, Kallol, Philouze, Christian, de Visser, Sam P., Gennari, Marcello, and Duboc, Carole. A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen.  Germany: N. p., 2017. 
Web.  doi:10.1002/anie.201703215.

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                    Brazzolotto, Deborah, Cantú Reinhard, Fabián G., Smith‐Jones, Julian, Retegan, Marius, Amidani, Lucia, Faponle, Abayomi S., Ray, Kallol, Philouze, Christian, de Visser, Sam P., Gennari, Marcello, & Duboc, Carole. A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen.  Germany.  https://doi.org/10.1002/anie.201703215

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                    Brazzolotto, Deborah, Cantú Reinhard, Fabián G., Smith‐Jones, Julian, Retegan, Marius, Amidani, Lucia, Faponle, Abayomi S., Ray, Kallol, Philouze, Christian, de Visser, Sam P., Gennari, Marcello, and Duboc, Carole. Fri .  
"A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen".  Germany.  https://doi.org/10.1002/anie.201703215.

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@article{osti_1401557,

  title        = {A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen},

  author       = {Brazzolotto, Deborah and Cantú Reinhard, Fabián G. and Smith‐Jones, Julian and Retegan, Marius and Amidani, Lucia and Faponle, Abayomi S. and Ray, Kallol and Philouze, Christian and de Visser, Sam P. and Gennari, Marcello and Duboc, Carole},

  abstractNote = {Abstract This study deals with the unprecedented reactivity of dinuclear non‐heme Mn II –thiolate complexes with O 2 , which dependent on the protonation state of the initial Mn II dimer selectively generates either a di‐μ‐oxo or μ‐oxo‐μ‐hydroxo Mn IV complex. Both dimers have been characterized by different techniques including single‐crystal X‐ray diffraction and mass spectrometry. Oxygenation reactions carried out with labeled 18 O 2 unambiguously show that the oxygen atoms present in the Mn IV dimers originate from O 2 . Based on experimental observations and DFT calculations, evidence is provided that these Mn IV species comproportionate with a Mn II precursor to yield μ‐oxo and/or μ‐hydroxo Mn III dimers. Our work highlights the delicate balance of reaction conditions to control the synthesis of non‐heme high‐valent μ‐oxo and μ‐hydroxo Mn species from Mn II precursors and O 2 .},

  doi          = {10.1002/anie.201703215},

  journal      = {Angewandte Chemie (International Edition)},

  number       = 28,

  volume       = 56,

  place        = {Germany},

  year         = {Fri Jun 09 00:00:00 EDT 2017},

  month        = {Fri Jun 09 00:00:00 EDT 2017}

}

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Works referenced in this record:

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction
journal, February 2016

Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol
Chemical Reviews, Vol. 116, Issue 6
DOI: 10.1021/acs.chemrev.5b00462

Structural and Magnetic Effects of Successive Protonations of Oxo Bridges in High-Valent Manganese Dimers
journal, December 1994

Baldwin, Michael J.; Stemmler, Timothy L.; Riggs-Gelasco, Pamela J.
Journal of the American Chemical Society, Vol. 116, Issue 25
DOI: 10.1021/ja00104a014

Oxygen activation by mononuclear Mn, Co, and Ni centers in biology and synthetic complexes
journal, November 2016

Fiedler, Adam T.; Fischer, Anne A.
JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3
DOI: 10.1007/s00775-016-1402-7

High-valent copper in biomimetic and biological oxidations
journal, December 2016

Keown, William; Gary, J. Brannon; Stack, T. Daniel P.
JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3
DOI: 10.1007/s00775-016-1420-5

Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction
journal, July 2016

Barman, Prasenjit; Upadhyay, Pranav; Faponle, Abayomi S.
Angewandte Chemie, Vol. 128, Issue 37
DOI: 10.1002/ange.201604412

Role of Proton-Coupled Electron Transfer in O–O Bond Activation
journal, July 2007

Rosenthal, Joel; Nocera, Daniel G.
Accounts of Chemical Research, Vol. 40, Issue 7
DOI: 10.1021/ar7000638

Copper–Oxygen Complexes Revisited: Structures, Spectroscopy, and Reactivity
journal, January 2017

Elwell, Courtney E.; Gagnon, Nicole L.; Neisen, Benjamin D.
Chemical Reviews, Vol. 117, Issue 3
DOI: 10.1021/acs.chemrev.6b00636

O ₂ Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex
journal, December 2015

Deville, Claire; Padamati, Sandeep K.; Sundberg, Jonas
Angewandte Chemie, Vol. 128, Issue 2
DOI: 10.1002/ange.201508372

Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol
journal, June 2015

Gennari, Marcello; Brazzolotto, Deborah; Pécaut, Jacques
Journal of the American Chemical Society, Vol. 137, Issue 26
DOI: 10.1021/jacs.5b04917

Dioxygen Binding, Activation, and Reduction to H ₂ O by Cu Enzymes
journal, June 2016

Solomon, Edward I.
Inorganic Chemistry, Vol. 55, Issue 13
DOI: 10.1021/acs.inorgchem.6b01034

Manganese Clusters with Relevance to Photosystem II
journal, September 2004

Mukhopadhyay, Sumitra; Mandal, Sanjay K.; Bhaduri, Sumit
Chemical Reviews, Vol. 104, Issue 9
DOI: 10.1021/cr0206014

Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst
journal, May 2015

McCann, Scott D.; Stahl, Shannon S.
Accounts of Chemical Research, Vol. 48, Issue 6
DOI: 10.1021/acs.accounts.5b00060

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective
journal, August 2016

Sahu, Sumit; Goldberg, David P.
Journal of the American Chemical Society, Vol. 138, Issue 36
DOI: 10.1021/jacs.6b05251

Biomimetic Oxygen Reduction by Cofacial Porphyrins at a Liquid–Liquid Interface
journal, March 2012

Peljo, Pekka; Murtomäki, Lasse; Kallio, Tanja
Journal of the American Chemical Society, Vol. 134, Issue 13
DOI: 10.1021/ja3004914

The Protonation States of Oxo-Bridged Mn ^IV Dimers Resolved by Experimental and Computational Mn K Pre-Edge X-ray Absorption Spectroscopy
journal, October 2013

Krewald, Vera; Lassalle-Kaiser, Benedikt; Boron, Thaddeus T.
Inorganic Chemistry, Vol. 52, Issue 22
DOI: 10.1021/ic4008203

Oxidationsreaktionen mit bioinspirierten einkernigen Nicht-Häm-Oxidometallkomplexen
journal, June 2016

Engelmann, Xenia; Monte-Pérez, Inés; Ray, Kallol
Angewandte Chemie, Vol. 128, Issue 27
DOI: 10.1002/ange.201600507

Synthetic Heme/Copper Assemblies: Toward an Understanding of Cytochrome c Oxidase Interactions with Dioxygen and Nitrogen Oxides
journal, July 2015

Hematian, Shabnam; Garcia-Bosch, Isaac; Karlin, Kenneth D.
Accounts of Chemical Research, Vol. 48, Issue 8
DOI: 10.1021/acs.accounts.5b00265

Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes ^†
journal, October 2004

Adler, Stuart B.
Chemical Reviews, Vol. 104, Issue 10
DOI: 10.1021/cr020724o

Electron-Transfer Reduction of Dinuclear Copper Peroxo and Bis-μ-oxo Complexes Leading to the Catalytic Four-Electron Reduction of Dioxygen to Water
journal, January 2012

Tahsini, Laleh; Kotani, Hiroaki; Lee, Yong-Min
Chemistry - A European Journal, Vol. 18, Issue 4
DOI: 10.1002/chem.201103215

Preface: Forum on Dioxygen Activation and Reduction
journal, April 2010

Tolman, William B.; Solomon, Edward I.
Inorganic Chemistry, Vol. 49, Issue 8
DOI: 10.1021/ic100161a

Singlet versus Triplet Reactivity in an Mn(V)–Oxo Species: Testing Theoretical Predictions Against Experimental Evidence
journal, September 2016

Yang, Tzuhsiung; Quesne, Matthew G.; Neu, Heather M.
Journal of the American Chemical Society, Vol. 138, Issue 38
DOI: 10.1021/jacs.6b05027

High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy
journal, January 2013

McDonald, Aidan R.; Que, Lawrence
Coordination Chemistry Reviews, Vol. 257, Issue 2
DOI: 10.1016/j.ccr.2012.08.002

Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction
journal, July 2016

Barman, Prasenjit; Upadhyay, Pranav; Faponle, Abayomi S.
Angewandte Chemie International Edition, Vol. 55, Issue 37
DOI: 10.1002/anie.201604412

Synthetic Mononuclear Nonheme Iron–Oxygen Intermediates
journal, July 2015

Nam, Wonwoo
Accounts of Chemical Research, Vol. 48, Issue 8
DOI: 10.1021/acs.accounts.5b00218

Activation of dioxygen by copper metalloproteins and insights from model complexes
journal, December 2016

Quist, David A.; Diaz, Daniel E.; Liu, Jeffrey J.
JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3
DOI: 10.1007/s00775-016-1415-2

Proton-Coupled Electron Transfer in Cytochrome Oxidase
journal, December 2010

Kaila, Ville R. I.; Verkhovsky, Michael I.; Wikström, Mårten
Chemical Reviews, Vol. 110, Issue 12
DOI: 10.1021/cr1002003

Mechanism of Four-Electron Reduction of Dioxygen to Water by Ferrocene Derivatives in the Presence of Perchloric Acid in Benzonitrile, Catalyzed by Cofacial Dicobalt Porphyrins
journal, August 2004

Fukuzumi, Shunichi; Okamoto, Ken; Gros, Claude P.
Journal of the American Chemical Society, Vol. 126, Issue 33
DOI: 10.1021/ja048403c

Status of Reactive Non-Heme Metal–Oxygen Intermediates in Chemical and Enzymatic Reactions
journal, August 2014

Ray, Kallol; Pfaff, Florian Felix; Wang, Bin
Journal of the American Chemical Society, Vol. 136, Issue 40
DOI: 10.1021/ja507807v

Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes
journal, June 2016

Engelmann, Xenia; Monte-Pérez, Inés; Ray, Kallol
Angewandte Chemie International Edition, Vol. 55, Issue 27
DOI: 10.1002/anie.201600507

Transition Metal Complexes and the Activation of Dioxygen
book, December 2014

Yee, Gereon M.; Tolman, William B.
Sustaining Life on Planet Earth: Metalloenzymes Mastering Dioxygen and Other Chewy Gases
DOI: 10.1007/978-3-319-12415-5_5

O ₂ Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex
journal, December 2015

Deville, Claire; Padamati, Sandeep K.; Sundberg, Jonas
Angewandte Chemie International Edition, Vol. 55, Issue 2
DOI: 10.1002/anie.201508372

Preparation and Properties of a Monomeric Mn ^IV −Oxo Complex
journal, July 2006

Parsell, Trenton H.; Behan, Rachel K.; Green, Michael T.
Journal of the American Chemical Society, Vol. 128, Issue 27
DOI: 10.1021/ja062332v

O ₂ Activation by Non-Heme Iron Enzymes
journal, November 2016

Solomon, Edward I.; Goudarzi, Serra; Sutherlin, Kyle D.
Biochemistry, Vol. 55, Issue 46
DOI: 10.1021/acs.biochem.6b00635

Activation of C−H Bonds by Metal Complexes
journal, December 1997

Shilov, Alexander E.; Shul'pin, Georgiy B.
Chemical Reviews, Vol. 97, Issue 8
DOI: 10.1021/cr9411886

Dioxygen Activation at Mononuclear Nonheme Iron Active Sites: Enzymes, Models, and Intermediates
journal, February 2004

Costas, Miquel; Mehn, Mark P.; Jensen, Michael P.
Chemical Reviews, Vol. 104, Issue 2
DOI: 10.1021/cr020628n

Characterization of Metastable Intermediates Formed in the Reaction between a Mn(II) Complex and Dioxygen, Including a Crystallographic Structure of a Binuclear Mn(III)–Peroxo Species
journal, April 2013

Coggins, Michael K.; Sun, Xianru; Kwak, Yeonju
Journal of the American Chemical Society, Vol. 135, Issue 15
DOI: 10.1021/ja311166u

Homogeneous catalytic O2 reduction to water by a cytochrome c oxidase model with trapping of intermediates and mechanistic insights
journal, August 2011

Halime, Z.; Kotani, H.; Li, Y.
Proceedings of the National Academy of Sciences, Vol. 108, Issue 34
DOI: 10.1073/pnas.1104698108

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Title: A High‐Valent Non‐Heme μ‐Oxo Manganese(IV) Dimer Generated from a Thiolate‐Bound Manganese(II) Complex and Dioxygen

Abstract

Citation Formats

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction journal, February 2016

Structural and Magnetic Effects of Successive Protonations of Oxo Bridges in High-Valent Manganese Dimers journal, December 1994

Oxygen activation by mononuclear Mn, Co, and Ni centers in biology and synthetic complexes journal, November 2016

High-valent copper in biomimetic and biological oxidations journal, December 2016

Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction journal, July 2016

Role of Proton-Coupled Electron Transfer in O–O Bond Activation journal, July 2007

Copper–Oxygen Complexes Revisited: Structures, Spectroscopy, and Reactivity journal, January 2017

O 2 Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex journal, December 2015

Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol journal, June 2015

Dioxygen Binding, Activation, and Reduction to H 2 O by Cu Enzymes journal, June 2016

Manganese Clusters with Relevance to Photosystem II journal, September 2004

Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst journal, May 2015

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective journal, August 2016

Biomimetic Oxygen Reduction by Cofacial Porphyrins at a Liquid–Liquid Interface journal, March 2012

The Protonation States of Oxo-Bridged Mn IV Dimers Resolved by Experimental and Computational Mn K Pre-Edge X-ray Absorption Spectroscopy journal, October 2013

Oxidationsreaktionen mit bioinspirierten einkernigen Nicht-Häm-Oxidometallkomplexen journal, June 2016

Synthetic Heme/Copper Assemblies: Toward an Understanding of Cytochrome c Oxidase Interactions with Dioxygen and Nitrogen Oxides journal, July 2015

Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes † journal, October 2004

Electron-Transfer Reduction of Dinuclear Copper Peroxo and Bis-μ-oxo Complexes Leading to the Catalytic Four-Electron Reduction of Dioxygen to Water journal, January 2012

Preface: Forum on Dioxygen Activation and Reduction journal, April 2010

Singlet versus Triplet Reactivity in an Mn(V)–Oxo Species: Testing Theoretical Predictions Against Experimental Evidence journal, September 2016

High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy journal, January 2013

Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction journal, July 2016

Synthetic Mononuclear Nonheme Iron–Oxygen Intermediates journal, July 2015

Activation of dioxygen by copper metalloproteins and insights from model complexes journal, December 2016

Proton-Coupled Electron Transfer in Cytochrome Oxidase journal, December 2010

Mechanism of Four-Electron Reduction of Dioxygen to Water by Ferrocene Derivatives in the Presence of Perchloric Acid in Benzonitrile, Catalyzed by Cofacial Dicobalt Porphyrins journal, August 2004

Status of Reactive Non-Heme Metal–Oxygen Intermediates in Chemical and Enzymatic Reactions journal, August 2014

Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes journal, June 2016

Transition Metal Complexes and the Activation of Dioxygen book, December 2014

O 2 Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex journal, December 2015

Preparation and Properties of a Monomeric Mn IV −Oxo Complex journal, July 2006

O 2 Activation by Non-Heme Iron Enzymes journal, November 2016

Activation of C−H Bonds by Metal Complexes journal, December 1997

Dioxygen Activation at Mononuclear Nonheme Iron Active Sites: Enzymes, Models, and Intermediates journal, February 2004

Characterization of Metastable Intermediates Formed in the Reaction between a Mn(II) Complex and Dioxygen, Including a Crystallographic Structure of a Binuclear Mn(III)–Peroxo Species journal, April 2013

Homogeneous catalytic O2 reduction to water by a cytochrome c oxidase model with trapping of intermediates and mechanistic insights journal, August 2011

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction
journal, February 2016

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journal, December 1994

Oxygen activation by mononuclear Mn, Co, and Ni centers in biology and synthetic complexes
journal, November 2016

High-valent copper in biomimetic and biological oxidations
journal, December 2016

Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction
journal, July 2016

Role of Proton-Coupled Electron Transfer in O–O Bond Activation
journal, July 2007

Copper–Oxygen Complexes Revisited: Structures, Spectroscopy, and Reactivity
journal, January 2017

O ₂ Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex
journal, December 2015

Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol
journal, June 2015

Dioxygen Binding, Activation, and Reduction to H ₂ O by Cu Enzymes
journal, June 2016

Manganese Clusters with Relevance to Photosystem II
journal, September 2004

Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst
journal, May 2015

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective
journal, August 2016

Biomimetic Oxygen Reduction by Cofacial Porphyrins at a Liquid–Liquid Interface
journal, March 2012

The Protonation States of Oxo-Bridged Mn ^IV Dimers Resolved by Experimental and Computational Mn K Pre-Edge X-ray Absorption Spectroscopy
journal, October 2013

Oxidationsreaktionen mit bioinspirierten einkernigen Nicht-Häm-Oxidometallkomplexen
journal, June 2016

Synthetic Heme/Copper Assemblies: Toward an Understanding of Cytochrome c Oxidase Interactions with Dioxygen and Nitrogen Oxides
journal, July 2015

Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes ^†
journal, October 2004

Electron-Transfer Reduction of Dinuclear Copper Peroxo and Bis-μ-oxo Complexes Leading to the Catalytic Four-Electron Reduction of Dioxygen to Water
journal, January 2012

Preface: Forum on Dioxygen Activation and Reduction
journal, April 2010

Singlet versus Triplet Reactivity in an Mn(V)–Oxo Species: Testing Theoretical Predictions Against Experimental Evidence
journal, September 2016

High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy
journal, January 2013

Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction
journal, July 2016

Synthetic Mononuclear Nonheme Iron–Oxygen Intermediates
journal, July 2015

Activation of dioxygen by copper metalloproteins and insights from model complexes
journal, December 2016

Proton-Coupled Electron Transfer in Cytochrome Oxidase
journal, December 2010

Mechanism of Four-Electron Reduction of Dioxygen to Water by Ferrocene Derivatives in the Presence of Perchloric Acid in Benzonitrile, Catalyzed by Cofacial Dicobalt Porphyrins
journal, August 2004

Status of Reactive Non-Heme Metal–Oxygen Intermediates in Chemical and Enzymatic Reactions
journal, August 2014

Oxidation Reactions with Bioinspired Mononuclear Non-Heme Metal-Oxo Complexes
journal, June 2016

Transition Metal Complexes and the Activation of Dioxygen
book, December 2014

O ₂ Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex
journal, December 2015

Preparation and Properties of a Monomeric Mn ^IV −Oxo Complex
journal, July 2006

O ₂ Activation by Non-Heme Iron Enzymes
journal, November 2016

Activation of C−H Bonds by Metal Complexes
journal, December 1997

Dioxygen Activation at Mononuclear Nonheme Iron Active Sites: Enzymes, Models, and Intermediates
journal, February 2004

Characterization of Metastable Intermediates Formed in the Reaction between a Mn(II) Complex and Dioxygen, Including a Crystallographic Structure of a Binuclear Mn(III)–Peroxo Species
journal, April 2013

Homogeneous catalytic O2 reduction to water by a cytochrome c oxidase model with trapping of intermediates and mechanistic insights
journal, August 2011