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Mechanistic Investigations on the Activation of Peroxides

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Mechanistic Investigations on the Activation of Peroxides MECHANISTIC INVESTIGATIONS ON THE ACTIVATION OF PEROXIDES BY MANGANESE COMPOUNDS MECHANISTISCHE UNTERSUCHUNGEN ZUR AKTIVIERUNG VON PEROXIDEN AN MANGANVERBINDUNGEN Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Sabine Rothbart aus Nürnberg Als Dissertation genehmigt von der naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 26.04.2012 Vorsitzender der Promotionskomission: Prof. Dr. Rainer Fink Erstberichterstatter: Prof. em. Dr. Dr. h. c. mult. Rudi van Eldik Zweitberichterstatterin: Prof. Dr. Ivana Ivanović-Burmazović Die vorliegende Arbeit entstand in der Zeit von September 2007 bis Februar 2012 am Department Chemie und Pharmazie der Friedrich-Alexander-Universität Erlangen Nürnberg. DANKSAGUNG Mein besonderer Dank gilt meinem Doktorvater Prof. em. Dr. Dr. h. c. mult. Rudi van Eldik für das große Interesse an meiner Arbeit und für zahlreiche wissenschaftliche Diskussionen. Außerdem möchte ich ihm besonders herzlich für die Möglichkeit danken, Teil seiner einmaligen Arbeitsgruppe und der Zaubervorlesung sein zu dürfen. Großen Dank schulde ich auch meinen Eltern, Sigrid und Günther Rothbart, für ihre konstante Unterstützung und ihren unerschütterlichen Glauben an mich. Des Weiteren möchte ich mich bei folgenden Leuten bedanken, die zum Gelingen dieser Arbeit beigetragen haben: Dr. Erika Ember für die Zusammenarbeit, Dr. Ralph Puchta für die DFT Rechnungen, Dr. Achim Zahl für NMR Messungen, Oliver Tröppner für die massenspektrometrischen Messungen, sowie Prof. U. Zenneck, Dr. Susanne Mossin und Dr. Jörg Sutter für die Einführung am EPR-Spektrometer. Prof. D. Chatterjee und seinem Team danke ich für die Durchführung der HPLC Analyse und gewinnbringende Diskussionen. Natürlich gebührt auch allen aktuellen und ehemaligen Mitgliedern der Arbeitsgruppe van Eldik ein herzliches und großes Danke für die angenehme Arbeitsatmosphäre, die stete Hilfsbereitschaft und den unglaublichen Zusammenhalt. Dies gilt insbesondere für: Ariane, Christoph, Matthias, Peter, Steffi, Lars, Raquel, Simon und Svetlana. Ihr tragt erheblich dazu bei, dass mir die Zeit meiner Promotion immer in besonders guter Erinnerung bleiben wird. Außerdem danke ich den fleißigen Zaubervorlesungs-Mitarbeitern der Arbeitskreise Burzlaff und Ivanović- Burmazović, sowie der Kaffeeraum-Crew für die gute Atmosphäre und Anita Schmitz für die schöne Zeit und gute Zusammenarbeit im Praktikum „AC-Explodieren“. Zu guter Letzt möchte ich besonders meinem Christoph sehr herzlich für die stete Unterstützung und seelische Kraft danken, die er mir während dieser Zeit gegeben hat. PUBLICATIONS AND CONFERENCE CONTRIBUTIONS PUBLICATIONS 1. Erika Ember, Sabine Rothbart, Ralph Puchta and Rudi van Eldik, “Metal – ion catalyzed oxidative degradation of Orange II by H2O2. High catalytic activity of simple manganese salts”, New J. Chem., 2009, 33, 34-49. The manuscript is featured on the cover of the January 2009 issue of the New Journal of Chemistry. 2. Sabine Rothbart, Erika Ember and Rudi van Eldik, “Comparative study of the catalytic activity of II III/IV [Mn (bpy)2Cl2] and [Mn2 (µ-O)2(bpy)4](ClO4)3 in the H2O2 induced oxidation of organic dyes in carbonate buffered aqueous solution”, Dalton Trans., 2010, 39, 3264-3272. 3. Erika Ember, Hanaa Gazzaz, Sabine Rothbart, Ralph Puchta and Rudi van Eldik, “MnII – a fascinating catalyst: Mechanistic insight into the catalyzed oxidative degradation of organic dyes by H2O2”, Appl. Catal. B., 2010, 95, 179-191. 4. Sabine Rothbart, Erika Ember and Rudi van Eldik, “Mechanistic studies on the oxidative degradation of Orange II by peracetic acid catalyzed by simple manganese(II) salts. Tuning the lifetime of the catalyst”, New J. Chem. 2012, 36, 732-748. 5. Sabine Rothbart and Rudi van Eldik, “Manganese compounds as versatile catalysts for the oxidative degradation of organic dyes”, Adv. Inorg. Chem. 2012, 65, submitted. ONGOING PROJECT Sabine Rothbart and Rudi van Eldik, “High catalytic activity of a Mn-terpy compound in oxidative dye degradation by peracetic acid”, in preparation. CONFERENCES AND WORKSHOPS POSTER. Oxidative degradation of Orange II by H2O2 catalyzed by divalent transition metals, Inorganic Reaction Mechanism Group Meeting (IRMG-36), March 2007, York, England. II III/IV POSTER. Catalytic activity of [Mn (bpy)2Cl2] and [Mn2 (µ-O)2(bpy)4](ClO4)3 in the H2O2 induced oxidation of organic dyes, Inorganic Reaction Mechanism Group Meeting (IRMG-39), January 2010, Kloster Banz, Germany. II POSTER. Mn – a fascinating oxidation catalyst: Mechanistic insight into the catalyzed oxidative degradation of organic dyes by H2O2, Inorganic Reaction Mechanism Group Meeting (IRMG- 39), January 2010, Kloster Banz, Germany. II III/IV ORAL PRESENTATION. Catalytic activity of [Mn (bpy)2Cl2] and [Mn2 (µ-O)2(bpy)4](ClO4)3 in the H2O2 induced oxidation of organic dyes, Erlangen-Kraków-Workshop on “Understanding the mechanisms of chemical processes”, May 2010, Kraków. LIST OF ABBREVIATIONS A absorbance AcOH acetic acid B / mT magnetic field in millitesla bpy 2,2’-bipyridine BHT 2,6-di-tert-butyl-4-methylphenol tBuOH tert-butanol c concentration CHES 2-(cyclohexylamino)ethanesulfonic acid CV cyclovoltammogram D value of the zero field splitting parameter DFT density functional theory DMSO-d6 hexadeuterodimethyl sulfoxide E / V potential in volts EPR electron paramagnetic resonance spectroscopy ES-MS electrospray mass spectrometry g g-faktor h Plank constant (6.62606885 · 10-34 J·s) h hour HEPES 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid I / A current in ampère I nuclear spin K equilibrium constant k rate constant kobs observed rate constant λ wavelength LMCT ligand-to-metal charge-transfer nm nanometer NMR nuclear magnetic resonance ν frequency Mo Morin; 2’,3,4’,5,7-Pentahydroxyflavone M mol/l Me3tacn 1,4,7-trimethyl-1,4,7-triazacyclononane OII Orange II; 4-(2-hydroxy-1-naphthylazo)benzenesulfonic acid sodium salt PAA peracetic acid phen 1,10-phenanthroline PNP p-nitrophenol, 1-hydroxy-4-nitrobenzol ppm parts per million S electron spin s second t time T temperature tacn 1,4,7-triazacyclononane TAPS [Tris(hydroxymethyl)methyl]aminopropanesulfonic acid TZ Tartrazine; trisodium (4E)-5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonato- phenyl)hydrazono]-3-pyrazolecarboxylate terpy 2,2':6',2"-terpyridine TOF turnover frequency (mol of dye oxidized by mol of catalyst per hour) TRIS 2-amino-2-hydroxymethylpropanediol UV/Vis ultraviolet-visible spectrophotometry TABLE OF CONTENTS 1 Introduction 1 1.1 TRANSITION METAL - MEDIATED OXIDATIVE BLEACH CATALYSIS 3 1.1.1 Iron-based bleaching catalysts 4 1.1.2 Manganese-based bleaching catalysts 5 1.2 OBJECTIVES 10 1.3 REFERENCES AND NOTES 12 2 Metal ion - catalyzed oxidative degradation of Orange II by H2O2. 17 2.1 GERNERAL REMARK 17 2.2 INTRODUCTION 17 2.3 RESULTS AND DISCUSSION 20 2.3.1 General observations 20 2.3.2 Complex-formation between Orange II and MnII 22 2.3.3 CV studies on the complex-formation between Orange II and MnII 26 2.3.4 DFT-calculations 27 2.3.5 Kinetic investigations 30 2.3.5.1 Complex-formation between bicarbonate and MnII 30 2.3.5.2 The effect of the total carbonate concentration 34 2.3.5.3 Reactivity profile as function of pH 39 II 2.3.5.4 Effect of the [Mn ] and [H2O2] on the oxidative reaction course 41 2.3.5.5 Stability of the in situ formed catalyst 44 2.3.6 Mechanistic aspects 45 2.4 CONCLUSIONS 48 2.5 EXPERIMENTAL SECTION 49 2.6 REFERENCES AND NOTES 52 3 Comparative study of a MnII-monomer and the corresponding III/IV oxo-bridged Mn2 -dimer 57 3.1 GENERAL REMARK 57 3.2 INTRODUCTION 57 3.3 RESULTS AND DISCUSSION 59 3.3.1 Kinetic measurements of the catalyzed dye degradation with H2O2 59 3.3.2 The reaction of the catalysts with H2O2 in carbonate buffered solution 65 3.3.2.1 EPR-spectroscopic measurements 65 3.3.2.2 UV/Vis spectroscopic measurements 67 3.3.3 In situ formation of the active species in the catalytic oxidation reaction 69 3.3.4 Precursor complex equilibria in solution 71 3.3.5 Mechanistic aspects 73 3.4 CONCLUSION 75 3.5 EXPERIMENTAL SECTION 75 3.6 REFERENCES AND NOTES 77 3.7 SUPPORTING INFORMATION 80 4 Metal ion - catalyzed oxidative degradation of Orange II by peracetic acid 85 4.1 GENERAL REMARK 85 4.2 INTRODUCTION 85 4.3 RESULTS AND DISCUSSION 87 4.3.1 Peracetic acid formation and its decomposition at higher pH 87 4.3.2 General observations 89 4.3.3 MnII + PAA – Intermediates formed in the absence of substrate 90 4.3.3.1 UV/Vis spectroscopy 90 4.3.3.2 EPR spectroscopy 97 4.3.4 Comparison of reactivity of different high valent oxo-manganese species with Orange II 100 4.3.5 Reactivity of different in situ formed intermediates towards Orange II 103 4.3.6 MnII catalyzed degradation of Orange II by PAA 107 4.3.7 Mechanistic interpretation 112 II II - 4.3.8 Comparison Mn /PAA vs. Mn /HCO4 system 116 4.4 CONCLUSIONS 118 4.5 EXPERIMENTAL SECTION 119 4.6 REFERENCES AND NOTES 121 4.7 SUPPLEMENTARY INFORMATION 126 5 High catalytic activity of a Mn-terpy compound in oxidative dye degradations with peracetic acid 141 5.1 GENERAL REMARK 141 5.2 INTRODUCTION 141 5.3 RESULTS AND DISCUSSION 143 5.3.1 MnII + terpy in solution 143 5.3.2 MnIIterpy + PAA in the absence of dye substrate 144 5.3.2.1 UV/Vis measurements 144 5.3.2.2 EPR measurements 147 5.3.3 MnIIterpy catalyzed dye degradation with PAA 149 5.3.3.1 General observations 149 5.3.3.2 Kinetics of the MnIIterpy catalyzed dye degradation by PAA 151 5.3.3.3 Readily prepared dimers in the catalytic dye degradation by PAA 156 5.3.4 Mechanistic implications 159 5.4 CONCLUSIONS 162 5.5 EXPERIMENTAL SECTION 163 5.6 REFERENCES AND NOTES 164 6 Summary 169 7 Zusammenfassung 177 1.
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