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Synthesis, Characterization and Reactivity of Functionalized Iron-Sulfur Clusters As Bioinspired Hydrogenase Models

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Synthesis, Characterization and Reactivity of Functionalized Iron-Sulfur Clusters As Bioinspired Hydrogenase Models Technisch-Naturwissenschaftliche Fakultät Synthesis, Characterization and Reactivity of Functionalized Iron-Sulfur Clusters as Bioinspired Hydrogenase Models DISSERTATION zur Erlangung des akademischen Grades Doktor der Technischen Wissenschaften im Doktoratsstudium der Technischen Wissenschaften Eingereicht von: DI Manuel Kaiser Angefertigt am: Institut für Anorganische Chemie Beurteilung: Prof. Dr. Günther Knör Assoc.-Prof. Mario Waser Mitwirkung: Linz, November 2015 Eidesstattliche Erklärung Ich erkläre an Eides statt, dass ich die vorliegende Dissertation selbstständig und ohne fremde Hilfe verfasst, andere als die angegebenen Quellen und Hilfsmittel nicht benutzt bzw. die wörtlich oder sinngemäß entnommenen Stellen als solche kenntlich gemacht habe. Die vorliegende Dissertation ist mit dem elektronisch übermittelten Textdokument identisch. Linz, November 2015 ________________________________ Manuel Kaiser I Dipl.‐Ing. Manuel Kaiser Persönliche Daten Geburtsdatum 15.11.1985 Staatsangehörigkeit Österreich Familienstand ledig Telefon 0699/12123124 Mail [email protected] Adresse Johann‐Wilhelm‐Klein‐Straße 2‐4, 4040 Linz Ausbildung 10/2012 – 12/2015 Doktoratsstudium Technische Wissenschaften, JKU Linz Dissertation am Institut für Anorganische Chemie betreut von Prof. Dr. Günther Knör: „Synthesis, Characterization and Reactivity of Functionalized Iron‐Sulfur Clusters as Bioinspired Hydrogenase Models“ 10/2005 – 09/2012 Diplomstudium Technische Chemie, JKU Linz (Abschluss: Dipl.‐Ing.) Diplomarbeit am Institut für Anorganische Chemie betreut von Dr. Uwe Monkowius: „Imidazol‐funktionalisierte Azobenzole als photoschaltbare N‐heterocyclische Carben‐Liganden“ 09/1996 – 07/2005 BRG Landwiedstraße, Linz (Abschluss: Matura) Grundwehrdienst 01/2005 – 09/2005 Jägerbataillon 12, Ostarrichikaserne, Amstetten Berufserfahrung 2011 Ferialarbeiter bei DSM Fine Chemicals Austria (jetzt: DPx Fine Chemicals), Linz 2006‐2010 Ferialarbeiter bei voestalpine Stahl, Linz Zusätzliche Qualifikation 2012‐2015 Präsentation von aktuellen Forschungsergebnissen bei nationalen und internationalen Konferenzen 2012‐2015 Tutoren‐ und Lektorentätigkeit bei mehreren Laborpraktika inklusive mehrmalige Organisation und Gesamtverantwortung II 2013‐2015 Teilnahme an Seminaren zur Weiterbildung: „Grundausbildung für NachwuchswissenschafterInnen“ „Studienrecht für Prüfende, Lehrende und Interessierte“ „Bei Stimme bleiben“ „Wirkung und Präsenz für Vorlesungen und Vorträge“ Fremdsprachen Englisch (verhandlungsfähig) EDV MS Office, ChemOffice, Citavi, Origin, TopSpin, GroupWise Hobbies Laufen, Kino, Lesen III Parts of this dissertation have already been published in peer‐reviewed journals or presented on national and international conferences as a poster or as a talk: Journal Articles M. Kaiser, G. Knör, Eur. J. Inorg. Chem. 2015, 25, 4199–4206. DOI: 10.1002/ejic.201500574 Talks 8. WACÖ (Workshop Anorganische Chemie Österreich, Salzburg, 14.‐15.04.2014) M. Kaiser, G. Knör: “Synthese und Charakterisierung mehrzähniger Schwefel‐Liganden für die Entwicklung neuer [FeFe]‐Hydrogenase Modellverbindungen” ISBOMC14 (7th International Symposium on Bioorganometallic Chemistry, Vienna, 22.‐25.07.2014) M. Kaiser, G. Knör: “Synthesis and Characterization of Bidentate Sulfur‐Ligands for the Development of Novel [FeFe]‐Hydrogenase Model Compounds” 16th Austrian Chemistry Days 2015 (Innsbruck, 21.‐23.09.2015) M. Kaiser, G.Knör: “Synthesis and Characterization of Iron‐Sulfur‐Clusters for the Development of Novel Hydrogenase Model Compounds” Poster presentations 9. Koordinationschemie‐Treffen (Bayreuth, 24.‐26.02.2013) M. Kaiser, G. Knör, U. Monkowius, C. Topf: “Synthesis and Characterization of a Modular Bridging Ligand Platform for Bio‐inspired Hydrogen Production” 15th Austrian Chemistry Days 2013 (Graz, 23.‐26.09.2013) M. Kaiser, G. Knör, U. Monkowius, C. Topf: “Synthesis and Characterization of novel heterodinuclear metal complexes for bio‐inspired hydrogen production” ISF‐1 & ISF‐1 Young (1st International Solar Fuels Conference & Symposium for Young Scientists, Uppsala, 24.04.‐01.05.2015) M. Kaiser, G. Knör: “Synthesis and Characterization of Iron‐Sulfur‐Clusters for the Development of Novel Hydrogenase Model Compounds” ICAME 2015 (International Conference on the Application of the Mössbauer Effect, Hamburg, 13.‐18.09.2015) M. Grodzicki, M. Kaiser, G. Knör, J. Schoiber, G. Tippelt: “Mössbauer Spectroscopy and Electronic Structure Calculations on the Trinuclear Iron Sulfur Cluster Fe3S2(CO)7dppm” IV Research Projects FWF Project (P25038) G. Knör, M. Kaiser, E. Kianfar: “Functional Light‐Responsive Metal Carbonyl Systems”, 2012‐2015. LaserLab Europe Project (llams_2062) G. Knör, M. Kaiser, S. Woutersen, S. Amirjalayer: “Unraveling the Mechanism of Fe‐based Photocatalytic Complexes for Solar Hydrogen Production”, 2014‐2015. V Kurzfassung Diese Dissertation behandelt das spannende Feld der Hydrogenase Modellverbindungen. Durch den steigenden Energiebedarf auf unserem Planeten ist es notwendig neue Wege zu beschreiten um diesem Bedarf gerecht zu werden. Eine Möglichkeit ist die Wasserstofferzeugung nach dem natürlichen Vorbild der Hydrogenasen. Besonders interessant ist die Möglichkeit ohne teure Edelmetalle wie Platin, welches nach wie vor hauptsächlich als Katalysator in der Industrie eingesetzt wird, auszukommen und stattdessen billige Metalle, die in reichlichem Ausmaß vorhanden sind, einsetzen zu können. Vorgestellt wird die Synthese und Charakterisierung zweier neuer [FeFe]‐Hydrogenase Modellverbindungen auf Basis von [3Fe2S] Clustern die mit Diphosphinen verbrückt sind. Im einfachsten Fall ist diese Brücke lediglich eine Methyleneinheit, eine weitere Verbindung wird durch das elektronenreiche Ferrocen verbrückt. Besonders wichtig ist dabei das elektrochemische und photochemische Verhalten zu unterscheiden. Daher konzentriert sich ein bedeutender Teil dieser Arbeit auf Belichtungsversuche und cylcovoltammetrische Untersuchungen bei unterschiedlichen Bedingungen. Um tatsächlich die Wasserstofferzeugung nachweisen zu können wurden zusätzlich Elektrolysen mit Headspace‐GC Analysen durchgeführt. Des Weiteren wurden auch weiterführende Untersuchungen wie Mößbauer Spektroskopie oder Messungen im Bereich der Ultrakurzzeit Spektroskopie mit Kollaborationen in Salzburg und Amsterdam durchgeführt. So konnte mit der vorliegenden Arbeit eine wichtige Grundlage für die Bereitstellung neuartiger auf Eisen basierter Katalysatorsysteme zur Gewinnung von Wasserstoff nach dem Vorbild der Natur gelegt werden wobei Teile dieser Arbeit bereits publiziert wurden. VI Abstract This dissertation covers the exciting field of hydrogenase model compounds. Due to the increasing energy demand on our planet, it is necessary to pursue new ways to satisfy this demand. One possibility is the generation of hydrogen as in natural hydrogenases. Of particular interest is the possibility to avoid expensive precious metals such as platinum, which is still the mainly used catalyst in industry, but instead to employ cheap earth‐abundant metals as catalysts. The syntheses and characterisation of two new [FeFe]‐hydrogenase model compounds based on a [3Fe2S] cluster bridged with diphosphines is presented. One compound is bridged by methylene, which is the simplest case and a second compound is bridged by the electron‐rich ferrocene subunit. It is especially important to differentiate between electrochemical and photochemical properties. For this reason, a substantial part of this work concentrates on irradiation experiments and investigations with cyclic voltammetry with variable parameters. To prove the hydrogen evolution, electrolysis with headspace‐GC analysis has been performed as well. Additionally, more advanced investigations such as Mössbauer spectroscopy or measurements in the field of ultrafast vibrational spectroscopy with collaborations in Salzburg and Amsterdam have been performed. The work presented here has built a foundation for the application of novel iron‐based catalyst systems developed for bioinspired generation of hydrogen. Parts of this work have already been published. VII Table of Contents 1 Introduction ..................................................................................................................................... 1 1.1 Hydrogen production .............................................................................................................. 1 1.2 Hydrogenases .......................................................................................................................... 2 1.2.1 The role of x‐ray crystallography ..................................................................................... 3 1.3 Hydrogenase Model compounds ............................................................................................ 4 1.4 Cyclic Voltammetry ................................................................................................................. 6 1.5 Mössbauer spectroscopy......................................................................................................... 6 1.6 Ultrafast vibrational spectroscopy .......................................................................................... 7 2 Practical Work ................................................................................................................................. 8 2.1 Objective.................................................................................................................................. 8 2.2 Alternatives ............................................................................................................................
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