European Journal of Inorganic Chemistry

Cover image for Vol. 2015 Issue 21

Special Issue: Biological Oxidation Reactions (Cluster Issue)

July 2015

Volume 2015, Issue 21

Pages 3352–3601

Issue edited by: Wesley R. Browne, Ebbe Nordlander

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
    1. You have free access to this content
      Artificial Diiron Enzymes with a De Novo Designed Four-Helix Bundle Structure (Eur. J. Inorg. Chem. 21/2015)

      Marco Chino, Ornella Maglio, Flavia Nastri, Vincenzo Pavone, William F. DeGrado and Angela Lombardi

      Article first published online: 28 JUL 2015 | DOI: 10.1002/ejic.201590084

      Thumbnail image of graphical abstract

      The front cover picture shows a construction site where workers are building up a four-helix bundle scaffold. A protein designer, working like an architect, has to adjust each minimal structural element in order to build up a stable and functional model. The metal site in the helical bundle scaffold represents the heart of the construction. Fine-tuning of the metal binding site enables a specific function, such as oxidative chemistry. This approach has been successfully employed to develop diiron–oxo protein models. Details are presented in the Microreview by A. Lombardi et al. on p. 3371 ff. For more on the story behind the cover research, see the Cover Profile.

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      Modelling Binuclear Metallobiosites: Insights from Pyrazole-Supported Biomimetic and Bioinspired Complexes (Eur. J. Inorg. Chem. 21/2015)

      Kristian E. Dalle and Franc Meyer

      Article first published online: 28 JUL 2015 | DOI: 10.1002/ejic.201590085

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      The back cover picture shows the overlap between natural metallobiosites and synthetic pyrazolato-based model complexes with respect to their ability to activate ubiquitous small molecules, such as dioxygen and water. The crystal structures illustrate this activation, depicting the peroxide-bound form of hemocyanin and the hydroxide-bridged configuration of phosphotriesterase, as well as the central coordination motifs in the two corresponding pyrazole-supported biomimetic complexes. Insights derived from studying such models of these and related binuclear metalloproteins are relevant in fields ranging from biological to inorganic and medicinal chemistry, and in catalysis research. Details are presented in the Microreview by K. E. Dalle and F. Meyer on p. 3391 ff.

  2. Cover Profile

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
    1. You have free access to this content
      Artificial Diiron Enzymes with a De Novo Designed Four-Helix Bundle Structure (page 3352)

      Marco Chino, Ornella Maglio, Flavia Nastri, Vincenzo Pavone, William F. DeGrado and Angela Lombardi

      Article first published online: 28 JUL 2015 | DOI: 10.1002/ejic.201500745

      Thumbnail image of graphical abstract

      The road to construct molecules that function as environmentally safe catalysts and biosensing devices is now open...

      Read more about the story behind the cover in the Cover Profile and about the research itself on p. 3371 ff.

  3. Editorial

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
    1. Editorial

      You have free access to this content
      Biological Oxidation Reactions (page 3353)

      Preeti Vashi

      Article first published online: 28 JUL 2015 | DOI: 10.1002/ejic.201500746

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      EurJIC, with Guest Editors Ebbe Nordlander and Wesley Browne, offers a collection of high-quality papers clustered around the theme Biological Oxidation Reactions – Mechanisms and Design of New Catalysts. This cluster issue is based on the COST Action CM1003 with the same name and presents the advances in designing new biological, biomimetic and bioinspired catalysts.

  4. Guest Editorial

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
    1. Biological Oxidation Reactions

      Biological Oxidation Reactions – Mechanisms and Design of New Catalysts (pages 3354–3356)

      Wesley R. Browne and Ebbe Nordlander

      Article first published online: 28 JUL 2015 | DOI: 10.1002/ejic.201500747

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      An overview of the papers in this cluster issue is presented. “Biological oxidation reactions utilising dioxygen, superoxide or hydrogen peroxide as oxidants are amongst the most ubiquitous of metal-catalysed reactions in biology. Over the last four years, the COST action CM1003 ‘Biological Oxidation Reactions – Mechanisms and Design of New Catalysts’ has brought together over 150 researchers from over 18 European countries to exchange ideas and collaborate on answering key questions facing the field.”

  5. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
  6. News

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
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    11. Full Papers
  7. Masthead

    1. Top of page
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    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
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    11. Full Papers
    1. Masthead: Eur. J. Inorg. Chem. 21/2015 (pages 3369–3370)

      Article first published online: 28 JUL 2015 | DOI: 10.1002/ejic.201590083

  8. Microreviews

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
    1. Artificial Enzymes

      Artificial Diiron Enzymes with a De Novo Designed Four-Helix Bundle Structure (pages 3371–3390)

      Marco Chino, Ornella Maglio, Flavia Nastri, Vincenzo Pavone, William F. DeGrado and Angela Lombardi

      Article first published online: 6 JUL 2015 | DOI: 10.1002/ejic.201500470

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      The de novo design of nature-inspired four-helix bundle metalloproteins is discussed. Special attention is given to the rational refinement of structure/function in diiron–oxo protein models from the due ferri family, which has allowed a shift from structural to functional models.

    2. Modelling Metallobiosites

      Modelling Binuclear Metallobiosites: Insights from Pyrazole-Supported Biomimetic and Bioinspired Complexes (pages 3391–3405)

      Kristian E. Dalle and Franc Meyer

      Article first published online: 2 JUN 2015 | DOI: 10.1002/ejic.201500185

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      Metalloenzymes with binuclear active sites are widespread in Nature. Synthetic modelling of these active sites has helped to highlight important structural and functional aspects which can dictate reactivity, providing blueprints for the development of new bioinspired catalysts. This microreview focuses on biologically relevant insights provided by complexes of 3,5-disubstitued pyrazole ligands.

    3. Artificial Metalloenzymes

      Latest Developments in Metalloenzyme Design and Repurposing (pages 3406–3418)

      Tillmann Heinisch and Thomas R. Ward

      Article first published online: 18 JUN 2015 | DOI: 10.1002/ejic.201500408

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      Artificial metalloenzymes (AMEs) combine homogeneous catalysis with enzymatic catalysis. In this microreview the authors describe recent developments in this fascinating field, ranging from artificial zinc hydrolases, metathesases, new heme protein reactions to light-driven redox reactions and enzyme models.

    4. Diiron Monooxygenases

      Controlling the Activities of the Diiron Centre in Bacterial Monooxygenases: Lessons from Mutagenesis and Biodiversity (pages 3419–3431)

      Tim Nichol, J. Colin Murrell and Thomas J. Smith

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500043

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      The soluble diiron monooxygenases (SDIMOs) are a diverse group of enzymes that use a diiron active centre to add oxygen to a wide range of organic molecules. Here we review how natural biodiversity and laboratory mutagenesis studies have revealed how the protein scaffold of SDIMOs controls the activity of the enzymes and the presentation of substrates to the diiron site.

    5. Mn Oxidation Catalysis

      Redox-State Dependent Ligand Exchange in Manganese-Based Oxidation Catalysis (pages 3432–3456)

      Shaghayegh Abdolahzadeh, Johannes W. de Boer and Wesley R. Browne

      Article first published online: 30 JUN 2015 | DOI: 10.1002/ejic.201500134

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      The role played by Mn-based complexes in controlling reactive oxygen species and in the water oxidation complex of photosystem II has inspired the design of catalysts for chemical processes such as the oxidation of organic substrates and bleaching applications. Here, the redox and pH dependence of the coordination chemistry of Mn complexes applied in oxidations with H2O2 is reviewed.

  9. Short Communications

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
    1. Polyoxometalate Catalysts

      Viral Nanotemplates Armed with Oxygenic Polyoxometalates for Hydrogen Peroxide Detoxification (pages 3457–3461)

      Debora Vilona, Antonio Sorarù, Chiara Maccato, Rossella Bortolaso, Livio Trainotti, Federica Valentini, Aldrei Boaretto, Cinzia Cepek, Marcella Bonchio and Mauro Carraro

      Article first published online: 22 APR 2015 | DOI: 10.1002/ejic.201500155

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      A polyoxometalate with oxygenic activity was anchored on the TMV (tobacco mosaic virus). The rod-like biogenic template enables the formation of catalytic nanoarrays for H2O2 dismutation.

    2. Cleavage of Polyenes

      Regioselective Cleavage of Electron-Rich Double Bonds in Dienes to Carbonyl Compounds with [Fe(OTf)2(mix-BPBP)] and a Combination of H2O2 and NaIO4 (pages 3462–3466)

      Peter Spannring, Vital A. Yazerski, Jianming Chen, Matthias Otte, Bert M. Weckhuysen, Pieter C. A. Bruijnincx and Robertus J. M. Klein Gebbink

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500213

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      The combination of an Fe-based catalyst, [Fe(OTf)2(mix-BPBP)], and the oxidants H2O2 and NaIO4 can discriminate between electronically different double bonds and oxidatively cleave the electron-rich bond in dienes to yield aldehydes and ketones in a regioselective manner. The reaction requires mild conditions (0–50 °C) and short reaction times (70 min).

  10. Full Papers

    1. Top of page
    2. Cover Picture
    3. Cover Profile
    4. Editorial
    5. Guest Editorial
    6. Graphical Abstract
    7. News
    8. Masthead
    9. Microreviews
    10. Short Communications
    11. Full Papers
    1. Water Oxidation

      A Bioinspired System for Light-Driven Water Oxidation with a Porphyrin Sensitizer and a Tetrametallic Molecular Catalyst (pages 3467–3477)

      Mirco Natali, Elisa Deponti, Debora Vilona, Andrea Sartorel, Marcella Bonchio and Franco Scandola

      Article first published online: 8 APR 2015 | DOI: 10.1002/ejic.201500063

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      The photoinduced events and the light-driven water-oxidation ability of a bioinspired, three-component catalyst/photosensitizer/acceptor molecular system are investigated.

    2. Oxidase and Catalase Mimics

      Mononuclear Iron(III) Complexes as Functional Models of Catechol Oxidases and Catalases (pages 3478–3484)

      Elena Badetti, Blerina Gjoka, Eszter Márta Nagy, Gérald Bernardinelli, Peter E. Kündig, Cristiano Zonta and Giulia Licini

      Article first published online: 16 FEB 2015 | DOI: 10.1002/ejic.201403225

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      Amino triphenolate iron(III) complexes promote effectively, at room temperature, the aerobic auto-oxidation of 3,5-di-tert-buthylcatechol to the corresponding o-benzoquinone (oxidase mimicking) and hydrogen peroxide dismutation (catalase mimicking).

    3. Catalase Mimics

      High Turnover Catalase Activity of a Mixed-Valence MnIIMnIII Complex with Terminal Carboxylate Donors (pages 3485–3492)

      Reena Singh, Matti Haukka, Christine J. McKenzie and Ebbe Nordlander

      Article first published online: 29 JUN 2015 | DOI: 10.1002/ejic.201500468

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      The neutral dimanganese(II,III) complex [Mn2(BCPMP)(OAc)2] (1) has been synthesized and characterized. Complex 1 was found to be an effective catalyst for the disproportionation of H2O2 with high catalytic rate and a turnover number of 7500, the highest turnover reported to date for a catalase mimic.

    4. Chiral Complexes for Oxidations

      Synthesis, Characterization, and Stereoselective Oxidations of the Dinuclear Copper(II) Complex Derived from a Chiral Diamino-m-xylenetetra(benzimidazole) Ligand (pages 3493–3500)

      Maria Lucia Perrone, Eliana Lo Presti, Simone Dell'Acqua, Enrico Monzani, Laura Santagostini and Luigi Casella

      Article first published online: 9 MAR 2015 | DOI: 10.1002/ejic.201500046

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      A dinuclear copper(II) complex derived from a chiral hexadentate nitrogen ligand is reported as a new catalyst for asymmetric oxidations. For biogenic catechols as model substrates, the best enantioselectivity is obtained in the oxidation of the methyl esters of L-/D-Dopa, for which 70 % ee is obtained in favor of the L enantiomer.

    5. Tyrosinase Models

      Catalytic Models of Tyrosinase: Reactivity Differences between Systems Based on Mono- and Binucleating Ligands (pages 3501–3511)

      Julia Schottenheim, Claus Gernert, Benjamin Herzigkeit, Jan Krahmer and Felix Tuczek

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500029

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      A tyrosinase model based on the binucleating ligand Lpy2 was developed and characterized. The ligand Lpy2 contains a combination of an imine and a pyridine function in the sidearms that are bridged by a flexible alkyl spacer. The Cu2Lpy2 complex catalyzes the conversion of monophenol DTBP-H into the o-quinone DTBQ (TON = 18). An electron-poor substrate is converted into the semiquinone.

    6. Copper Monooxygenase Models

      Synthesis and Characterization of a Dinuclear Copper Complex Bearing a Hydrophobic Cavity as a Model for Copper-Containing Monooxygenases (pages 3512–3518)

      Olivier Schicke, Bruno Faure, Yannick Carissan, Michel Giorgi, Ariane Jalila Simaan and Marius Réglier

      Article first published online: 3 JUN 2015 | DOI: 10.1002/ejic.201500280

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      The synthesis and characterization of a dinuclear copper complex as a model of mononuclear Cu-containing monooxygenases are described. This model exhibits features equivalent to those of the enzymes: (1) the two Cu centers are 11.5 Å apart and (2) there is a hydrophobic pocket consisting of a cyclophane moiety in which substrates can bind near the two Cu centers.

    7. V-Catalyzed Oxidative Bromination

      Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis (pages 3519–3525)

      Federica Sabuzi, Ekaterina Churakova, Pierluca Galloni, Ron Wever, Frank Hollmann, Barbara Floris and Valeria Conte

      Article first published online: 20 MAR 2015 | DOI: 10.1002/ejic.201500086

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      Catalysis of thymol bromination by vanadium derivatives is directly compared to catalysis by a V-dependent bromoperoxidase. All reactions were performed under mild and sustainable conditions with relatively inexpensive reagents. Appealing results were obtained in terms of selectivity and sustainability.

    8. Immobilized Biocatalysts

      The Electrically Wired Molybdenum Domain of Human Sulfite Oxidase is Bioelectrocatalytically Active (pages 3526–3531)

      Roberto Spricigo, Silke Leimkühler, Lo Gorton, Frieder W. Scheller and Ulla Wollenberger

      Article first published online: 31 MAR 2015 | DOI: 10.1002/ejic.201500034

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      Human sulfite oxidase and its catalytic molybdenum-cofactor-containing domain were wired to an electrode with poly(vinylpyridine)–[osmium(N,N′-methyl-2,2′-biimidazole)3]2+/3+, which mediated the electron transfer between either of the enzyme cofactors and the electrode, as demonstrated by electrocatalytic turnover currents.

    9. Mn Oxidation Catalysts

      Mechanistic Links in the in-situ Formation of Dinuclear Manganese Catalysts, H2O2 Disproportionation, and Alkene Oxidation (pages 3532–3542)

      Davide Angelone, Shaghayegh Abdolahzadeh, Johannes W. de Boer and Wesley R. Browne

      Article first published online: 21 APR 2015 | DOI: 10.1002/ejic.201500195

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      The in situ formation of catalytically active species through the reduction of a precatalyst, H2O2 disproportionation and alkene oxidation are linked to a common active species.

    10. Mn–Carboxylate Catalysts

      Too Many Cooks Spoil the Broth – Variable Potencies of Oxidizing Mn Complexes of a Hexadentate Carboxylato Ligand (pages 3543–3549)

      Claire Deville, Maik Finsel, David P. de Sousa, Barbara Szafranowska, Julian Behnken, Simon Svane, Andrew D. Bond, Rune Kirk Seidler-Egdal and Christine J. McKenzie

      Article first published online: 29 APR 2015 | DOI: 10.1002/ejic.201500210

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      A manganese(II) complex of a hexadentate ligand catalyzes epoxidation. However, reaction conditions are critical since several metal-based oxidants with varying potencies can be generated. This observation is probably general for related catalysts, and consequences include decreased selectivity and competing water oxidation.

    11. Redox-Active Molybdopterins

      Synthesis, Structure and Redox Properties of Asymmetric (Cyclopentadienyl)(ene-1,2-dithiolate)cobalt(III) Complexes Containing Phenyl, Pyridyl and Pyrazinyl Units (pages 3550–3561)

      James P. Dicks, Muhammad Zubair, E. Stephen Davies, C. David Garner, Carola Schulzke, Claire Wilson and Jonathan McMaster

      Article first published online: 22 APR 2015 | DOI: 10.1002/ejic.201500138

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      Structural, electrochemical, spectroscopic and theoretical studies of [(η5-C5H5)Co(dithiolene)] complexes suggest that the pyran ring-opened form of the molybdenum cofactor of Mo- and W-containing oxygen-atom-transfer enzymes may participate in the redox reactions involved in the catalytic cycle.

    12. Oxygen Atom Transfer

      Electronic Fine-Tuning of Oxygen Atom Transfer Reactivity of cis-Dioxomolybdenum(VI) Complexes with Thiosemicarbazone Ligands (pages 3562–3571)

      Aurélien Ducrot, Bethany Scattergood, Ben Coulson, Robin N. Perutz and Anne-K. Duhme-Klair

      Article first published online: 2 APR 2015 | DOI: 10.1002/ejic.201500059

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      Thiosemicarbazone ligands (H2LR) derived from para-substituted salicylaldehydes allow the electronic properties and catalytic activities of cis-dioxo MoVI complexes of composition [MoO2(LR)MeOH] to be fine-tuned by electron-donating or electron-withdrawing groups R.

    13. Dioxo-Mo and -W Catalysts

      Dioxomolybdenum(VI) and -tungsten(VI) Complexes with Multidentate Aminobisphenol Ligands as Catalysts for Olefin Epoxidation (pages 3572–3579)

      Antoine Dupé, Md. Kamal Hossain, Jörg A. Schachner, Ferdinand Belaj, Ari Lehtonen, Ebbe Nordlander and Nadia C. Mösch-Zanetti

      Article first published online: 27 APR 2015 | DOI: 10.1002/ejic.201500055

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      Four new molybdenum and tungsten complexes bearing tetradentate tripodal amino bisphenolate ligands with either hydroxyethylene or hydroxyglycolene substituents were synthesized and found to catalyze olefin epoxidation reactions under eco-friendly conditions.

    14. Oxygen Atom Transfer Reactions

      A Computational Comparison of Oxygen Atom Transfer Catalyzed by Dimethyl Sulf­oxide Reductase with Mo and W (pages 3580–3589)

      Jilai Li, Milica Andrejić, Ricardo A. Mata and Ulf Ryde

      Article first published online: 9 JUN 2015 | DOI: 10.1002/ejic.201500209

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      The dimethyl sulfoxide (DMSO) reductase reaction with Mo and W was studied by using 13 different DFT methods calibrated to accurate LCCSD(T0)/CBS energies. A two-step reaction was found, the second barrier being rate limiting. This barrier is about 28 kJ/mol lower for W than for Mo owing to a ca. 67 kJ/mol more exothermic reaction energy. The experimental activation enthalpy for Mo is reproduced within 5–9 kJ/mol.

    15. Iron Oxidation Catalysts

      Catalytic Oxidation of Alkanes and Alkenes by H2O2 with a μ-Oxido Diiron(III) Complex as Catalyst/Catalyst Precursor (pages 3590–3601)

      Biswanath Das, Afnan Al-Hunaiti, Matti Haukka, Serhiy Demeshko, Steffen Meyer, Albert A. Shteinman, Franc Meyer, Timo Repo and Ebbe Nordlander

      Article first published online: 17 JUL 2015 | DOI: 10.1002/ejic.201500576

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      A μ-oxido diiron(III) complex, [Fe2(μ-O)(LiDPCPMPP)2](ClO4)2, was synthesized and characterized. This complex was used as catalyst in C–H bond oxidation with CH3COOH–H2O2 as chemical oxidant. Reactivity studies indicate that the oxidation process goes through a metal-based mechanism concomitant with a radical process.

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