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Development of Tailored Homogeneous Ruthenium Catalysts for the Application in the Hydrogenation of Biogenic Substrates

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Development of Tailored Homogeneous Ruthenium Catalysts for the Application in the Hydrogenation of Biogenic Substrates Development of Tailored Homogeneous Ruthenium Catalysts for the Application in the Hydrogenation of Biogenic Substrates Entwicklung maßgeschneiderter homogener Ruthenium Katalysatoren für die Anwendung in der Hydrierung biogener Substrate Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der RWTH Aachen University zur Erlangung des akademischen Grades einer Doktorin der Naturwissenschaften genehmigte Dissertation vorgelegt von Celine Laura Jung M.Sc. RWTH aus Püttlingen Berichter: Prof. Dr. rer. nat. Jürgen Klankermayer Prof. Dr.-Ing. Andreas Jupke Tag der mündlichen Prüfung: 17.06.2020 Diese Dissertation ist auf den Internetseiten der Universitätsbibliothek verfügbar. Die experimentellen Arbeiten zur vorliegenden Dissertation wurden im Zeitraum von Januar 2016 bis November 2019 unter der wissenschaftlichen Anleitung von Prof. Dr. rer. nat. Jürgen Klankermayer am Institut für Technische und Makromolekulare Chemie (ITMC) der RWTH Aachen University angefertigt. i Eidesstattliche Erklärung Ich, Celine Laura Jung erkläre hiermit, dass diese Dissertation und die darin dargelegten Inhalte die eigenen sind und selbstständig, als Ergebnis der eigenen originären Forschung, generiert wurden. Hiermit erkläre ich an Eides statt 1. Diese Arbeit wurde vollständig oder größtenteils in der Phase als Doktorand dieser Fakultät und Universität angefertigt; 2. Sofern irgendein Bestandteil dieser Dissertation zuvor für einen akademischen Abschluss oder eine andere Qualifikation an dieser oder einer anderen Institution verwendet wurde, wurde dies klar angezeigt; 3. Wenn immer andere eigene- oder Veröffentlichungen Dritter herangezogen wurden, wurden diese klar benannt; 4. Wenn aus anderen eigenen- oder Veröffentlichungen Dritter zitiert wurde, wurde stets die Quelle hierfür angegeben. Diese Dissertation ist vollständig meine eigene Arbeit, mit der Ausnahme solcher Zitate; 5. Alle wesentlichen Quellen von Unterstützung wurden benannt; 6. Wenn immer ein Teil dieser Dissertation auf der Zusammenarbeit mit anderen basiert, wurde von mir klar gekennzeichnet, was von anderen und was von mir selbst erarbeitet wurde; 7. Ein Teil oder Teile dieser Arbeit wurden zuvor veröffentlicht und zwar in: Gordon Research Seminar and Gordon Research Conference 2018 Green Chemistry, Castelldefels, Spanien, 28. Juli–3. August 2018. Posterpräsentation “Novel Ruthenium Triphos Catalysts for the Hydrogenation of Methyl-γ-butyrolactones to 2-Methyl- butane-1,4-diol”, C. L. Jung, J. Klankermayer. 6th International Conference of the Cluster of Excellence “Tailor-Made Fuels from Biomass”, Aachen, Deutschland, 19.–21. Juni 2018. Posterpräsentation “Novel Ru- thenium Triphos Catalysts for the Hydrogenation of Itaconic Acid and Methyl-γ-butyro- lactones”, C. L. Jung, A. J. Schmitz, J. Klankermayer. Datum, Unterschrift ii Abstract The present thesis describes the development of tailored molecular ruthenium catalyst systems for the selective hydrogenation of biogenic platform chemicals. Chapter 1 provides an introduction on the state of the art in the synthesis of the two bio-based compounds levulinic and itaconic acid and their potential as renewable building blocks for future chemical value chains. Complementary, a short overview of homogeneous catalytic systems describes the challenges linked to the hydrogenation of acids and esters with special focus on ruthenium triphos systems. In Chapter 2, the development of a catalyst lead structure is explained, enabling the tailoring of molecular complexes for the catalytic application. In detail, the preparation of a series of ruthenium triphos-xyl complexes bearing acetato, naphtholato or phenolato ligands from [Ru(triphos-xyl)(tmm)] is described and completed with the characterization of the complex molecules. The subsequent results of the catalytic hydrogenation of levulinic acid and γ-valerolactone to 1,4-pentanediol by selected ruthenium triphos-xyl complexes are reported in Chapter 3. High activities at low catalyst concentrations could be observed in batch experiments and multiple substrate reloading cycles revealed a correlation of catalyst deactivation with thermal stress in the absence of substrate. Moreover, the successful dehydrogenation of 1,4-pentanediol to γ-valerolactone showed the presence of a dynamic lactone-diol equilibrium. NMR-spectroscopic investigations revealed the formation of a bis(levulinato) complex on dissolving the catalysts in levulinic acid prior to the hydrogenation. The challenging hydrogenation of itaconic acid, itaconates and 2-methyl-γ-butyrolactone to 2-methyl-1,4-butanediol with adapted ruthenium triphos-xyl complexes is reported in Chapter 4. Selected fluorinated phenolato and naphtholato ruthenium triphos-xyl catalyst systems showed significantly improved activities compared to established systems. Besides the fluorinated phenols, also hexafluorobenzene could be identified as beneficial additive leading to a closer investigation on its reactivity with [Ru(triphos-xyl)(tmm)] in Chapter 5. As a result, the dimeric fluorine-bridged complex [{Ru(triphos-xyl)}2(µ-F)3]+ could be isolated and successfully applied in the hydrogenation of selected acids, esters and amides. In particular, it was found to be active at very low catalyst concentrations in the hydrogenation of levulinic acid and γ-valerolactone. Moreover, an unprecedented complex with coordinated PF6− anion to the ruthenium center could be developed and characterized. iii Zusammenfassung Die vorliegende Arbeit beschreibt die Entwicklung maßgeschneiderter molekularer Ruthenium Katalysatoren für die selektive Hydrierung biogener Plattformchemikalien. In Kapitel 1 erfolgt eine Einführung in den aktuellen Stand der Herstellung der beiden biobasierten Verbindungen Levulinsäure und Itaconsäure und deren Potential als erneuerbare Bausteine für zukünftige chemische Wertschöpfungsketten. Ergänzend beschreibt ein kurzer Überblick über homogene Katalysatorsysteme, mit besonderem Fokus auf Ruthenium Triphos Systemen, die mit der Hydrierung von Säuren und Estern einhergehenden Herausforderungen. In Kapitel 2 wird die Entwicklung einer Katalysator-Leitstruktur beschrieben, welche das Maßschneidern von molekularen Komplexen für die Anwendung als Katalysatoren ermöglicht. Im Detail wird die Darstellung einer Reihe von Ruthenium Triphos-xyl Komplexen mit Acetato-, Naphtholato- oder Phenolatoliganden ausgehend von [Ru(triphos-xyl)(tmm)] beschrieben und mit der Charakterisierung der Komplexmoleküle komplettiert. Die folgenden Ergebnisse der katalytischen Hydrierung von Levulinsäure und γ-Valerolacton zu 1,4-Pentandiol mit ausgewählten Ruthenium Triphos-xyl Komplexen werden in Kapitel 3 berichtet. In Batch-Experimenten konnten hohe Aktivitäten bei niedriger Katalysatorkonzentration beobachtet werden und in mehreren Substratbeladungs-Zyklen wurde eine Korrelation zwischen der Katalysatordeaktivierung und der thermischen Belastung in Abwesenheit von Substrat beobachtet. Zudem zeigte die erfolgreiche Dehydrierung von 1,4-Pentandiol zu γ-Valerolacton das Auftreten eines dynamischen Lacton-Diol Gleichgewichts. NMR-spektroskopische Untersuchungen offenbarten die Bildung einer bis(levulinato) Spezies, die durch Lösen der Katalysatoren in Levulinsäure vor der Hydrierung gebildet wird. Die anspruchsvolle Hydrierung von Itaconsäure, Itaconaten und 2-Methyl-γ-butyrolacton zu 2-Methyl-1,4-butandiol mit geeigneten Ruthenium Triphos-xyl Komplexen wird in Kapitel 4 berichtet. Ausgewählte fluorierte Phenolato- und Naphtholato Ruthenium Triphos-xyl Katalysatoren zeigten signifikant verbesserte Aktivitäten im Vergleich zu etablierten Systemen. Neben den fluorierten Phenolen wurde auch Hexafluorobenzol als vorteilhaftes Additiv identifiziert, was zu einer näheren Betrachtung seiner Reaktivität mit [Ru(triphos-xyl)(tmm)] in Kapitel 5 führte. In Folge konnte das Fluor-verbrückte Dimer [{Ru(triphos-xyl)}2(µ-F)3]+ isoliert und erfolgreich in der Hydrierung ausgewählter Säuren, Ester und Amide eingesetzt werden. Im Besonderen konnte seine Aktivität in sehr niedrigen Katalysatorkonzentrationen in der Hydrierung von Levulinsäure und γ-Valerolacton genutzt werden. Zudem konnte ein neuartiger Komplex mit einem an das Rutheniumzentrum koordinierten PF6− Anion entwickelt und charakterisiert werden. iv Table of Contents Eidesstattliche Erklärung ............................................................................................................................................................................................................................................ ii Abstract ............................................................................................................................................................................................................................................................................. iii Zusammenfassung ........................................................................................................................................................................................................................................................ iv Table of Contents ............................................................................................................................................................................................................................................................ v List of Abbreviations ..................................................................................................................................................................................................................................................
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