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Unsymmetric Redoxactive Ligands for Mono- and Bimetallic Complexes; Synthesis and Characterisation

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Unsymmetric Redoxactive Ligands for Mono- and Bimetallic Complexes; Synthesis and Characterisation Technische Universität München Fachgebiet Bioanorganische Chemie Unsymmetric Redoxactive Ligands for Mono- and Bimetallic Complexes; Synthesis and Characterisation Ruth Marlen Haas Vollständiger Abdruck der von der Fakultät Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.) genehmigten Dissertation. Vorsitzende(r): Hon.-Prof. Dr. Richard W. Fischer Prüfer der Dissertation: 1. Prof. Dr. Corinna Hess 2. Prof. Dr. Klaus Köhler Die Dissertation wurde am 12.12.2017 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 16.01.2018 angenommen. Die vorliegende Arbeit wurde im Fachgebiet Bioanorganische Chemie der Technischen Universität München in der Zeit von November 2014 bis Dezember 2017 angefertigt. Teile dieser Arbeit wurden bereits veröffentlicht: Haas, R. M., Arshad, M., Anthony, J. A., Altmann, P. J., Pöthig, A., Köhler, F. H., Hess, C. R. “Six- and seven-coordinate Fe(II) and Zn(II) compounds ligated by unsymmetrical xanthene- based ligands: characterization and magnetic properties.” Inorg. Chem. Front., 2016, 3, 616. Haas, R. M., Hern, Z., Sproules, S., Hess, C. R. “An unsymmetric ligand framework for non- coupled homo- and heterobimetallic complexes.” Inorg. Chem., 2017, doi:10.1021/acs.inorgchem.7b02294. Besonders danken möchte ich meiner Doktormutter Frau Professor Corinna R. Hess Für die Aufnahme in den Lehrstuhl und das interessante Forschungsthema, welches mir vorgeschlagen wurde. Acknowledgment Mein Dank gilt: Meinem Mitstarter am Lehrstuhl Manuel Kaspar, der alles mit mir aufgebaut hat. Ich hätte es auch gerne mit dir beendet. Sophia Stark, die in der letzten Halbzeit eine großartige Rücken- an-Rücken Bürostuhlnachbarin war. Unsere Diskussionen waren immer sehr verwirrend, haben uns aber oft weitergebracht und auch die Kaffee-/Teepausen waren immer erholsam. Michael Grübel, der OCler, hat oft Chaos in unserem Labor verbreitet, uns aber auch mit organischen Reaktionen weitergeholfen, Ceren Tok, die neues Flair in unsere Gruppe gebracht hat ,sowie Andreas Hofmann, meinem Nachfolger und unserem Neuzugang Raphael Lauenstein. Unseren zwei Postdocs, Dr. Anica Dose und Dr. Daniel Betz, die uns jeweils ein Jahr begleitet haben, waren immer für gute Ratschläge zu haben. Pauline Fischer und Lukas Niederegger, unseren Masteranten, Auch wenn ich oft Recht hatte, ihr habt großartige Arbeit geleistet und unsere Gruppe bereichert. Dr. Alexander Pöthig, der mich in die Geheimnisse der Röntgenstrukturanalyse eingeführt hat und mit guten Ratschlägen weiterhelfen konnte. Außerdem gilt mein Dank seinem Kristallographieteam, allen voran Philipp Altmann, aber auch Christan Jandl und David Mayer. Danke für eure Hilfe, ich habe nicht aufgegeben. Dr. Gaby Raudaschl-Sieber und Dr. Markus Drees, die ich bei der Betreuung von Laborpraktika unterstützen konnte , von denen ich aber auch immer Hilfe und Ratschläge erhalten habe. Meinen Studenten, Fabian Hörmann, Lorenz Pardatscher, Zach Hern und David Müller, die mein Thema mit vorangebracht und oft für entscheidende Fortschritte durch ihre unermüdliche Arbeit gesorgt haben. Weiter möchte ich mich bei Dr. Lilian Graser bedanken. Sie hat mich zur metallorganischen Chemie gebracht und dafür begeistert. Sie war sowohl an der Universität als auch Privat eine großartige Persönlichkeit und ein Rückhalt. Das Gleiche gilt für Dr. Nadine Eckstein, die mir immer mit Rat und Tat zur Seite stand. Danken möchte ich den Mitarbeitern der Lehrstühle von Professor Kühn und Professor Fischer. Sie haben oft ausgeholfen und uns Geräte und Materialen zur Verfügung gestellt. vi Den Technikern, Jürgen Kudermann, Maria Weindl, Olaf Ackermann , Ulrike Ammari, Bircan Dilki, Petra Ankenbauer und Rodica Dumitrescu, die meine Proben immer zeitnah gemessen haben. Sie haben mir geduldig die Geräte erklärt und hatten Antworten auf meine Fragen. Frau Kullick, die unserem Lehrstuhl als Sekretärin beistand Sie hat uns entlastet und immer Antworten auf unsere Fragen gefunden. Aus meiner Studienzeit sind mir Christina Schwarzenböck, Susanne Herden und Lena Böbel in guter Erinnerung geblieben, ebenso unser Freitag-Mittagstisch, Johannes Stecher, Christoph Brenninger, Maike Wahl und Christine Hutterer. Zuletzt möchte ich meiner Familie danken, meiner Mama und meinem Papa, die mich immer unterstützt und mir das Studium ermöglichten. Sie haben frühzeitig dafür gesorgt, dass ich in verschiedene Bereiche der Chemie Einblicke erhielt. Meiner Schwester Sylvia und ihrem Mann Simon für die Fahrdienste nach München und unserem jüngsten Familienzuwachs Alexander, der für Unruhe sorgt. Der erweiterten Familie, meinem inzwischen leider verstorbenen Opa, meiner Oma, meinen Tanten, Onkel, Cousins und Cousinen, welche immer gefragt haben, wie es grad läuft. Michi möchte ich dafür danken, dass er immer zugehört hat, an meiner Seite war und mich auch mal abgelenkt hat vii Deutscher Abstract In der vorliegenden Arbeit wurden zwei Projekte bearbeitet deren Gemeinsamkeit ein nicht-redox-inertes Ligandensystem ist. Nicht-redox-inerte Ligandensysteme erfahren in den letzten Jahren mehr Aufmerksamkeit, da sie Multielektronenreaktionen unterstützen. Bei der Umsetzung oder Bildung kleiner Moleküle (wie CO2, H2 oder N2) sind Multielektronenreaktionen unumgänglich und werden daher intensiv erforscht. Die Aktivierung oder Umsetzung dieser Moleküle ist nötig aufgrund der wachsenden Bevölkerung und des damit verbundenen erhöhten Energiebedarfs und ermöglicht eine CO2 neutrale Energiespeicherung. In der Synthese der iXa und iXa-2 Liganden wurde eine nicht redox inerte Iminopyridine- Einheit eingebaut und die Eisen- und Zinkkomplexe dazu synthetisiert. Diese Komplexe wurden sowohl in Lösung, also auch im Feststoff, untersucht. Beide Komplexe konnten die Erwartungen an Redoxaktivität nur bedingt erfüllen, zeigten aber gerade in der Messung der magnetischen Suszeptibilität unerwartete Eigenschaften, welche einen möglichen Einsatz als magnetisches Material versprechen. Dafür wurden diese Komplexe noch genauer mit DFT- Rechnungen begutachtet und besonders für den ungewöhnlichen siebenfach koordinierten Fe(iXa)-Komplex, die Labilität der Liganden mit NMR-Spektroskopie untersucht. Der Versuch weiter Komplexe zu synthetisieren zeigt, dass das Ligandensystem nicht stabil gegenüber Nickelionen ist. Ein größerer Teil dieser Arbeit umfasste die Entwicklung und Synthese des Ligandengerüsts der Korbliganden, der offenen Korbliganden und des sogenannten PDIpCy- Liganden. Mit diesen Systemen wurden nicht-redox-inerte Koordinationsstellen mit einer redox-inerten Koordinationsstelle in einem Liganden für bimetallische Komplexe kombiniert. Das am besten untersuchte System ist bisher der PDIpCy- Ligand mit seinen Komplexen, da hier strukturelle Nachweise existieren. In vielen anderen Fällen konnte die Koordination eines zweiten Metalls nicht sicher bestätigt werden. Der PDIpCy-Ligand bildet sowohl homo- als auch heterobimetallische Komplexe. Ein Vorteil dieses Systems sind die zwei unterschiedlichen aber dennoch sehr räumlich klaren Bindungsstellen, welche, soweit bisher erforscht, nicht direkt miteinander interagieren. Die bisher synthetisierten Nickel, Zink und Eisenkomplexe müssen nun noch auf ihre Reaktivität untersucht werden. viii English Abstract In this work, two projects are presented based on redox-active ligand scaffolds. Over the last decades the non-innocent theory became more abundant as they support multi-electron reactions. Many reactions for the activation or formation of small molecules, like CO2, H2 or N2, include a multi-electron step. The work on small molecules gained importance as the growing population has a rising energy demand. In the first project, the iXa and iXa-2 ligands a non-innocent diimine moiety was incorporated into the ligand scaffolds and the iron and zinc complexes were isolated. The metal complexes were thoroughly examined in solution and in solid state. The redox-activity of the non-innocent complexes did not completely meet our expectation, but the measurement of the magnetic susceptibility gave surprising results, which need to be investigated for magnetic materials. Therefore, DFT calculations were set up and the ligand lability of the rare seven coordinate Fe(iXa)-complex was investigated by NMR spectroscopy. Further complex syntheses were set up with nickel ions, but showed that our ligand scaffold is not stable in reactions with nickel ions under applied conditions. The second project was the development and synthesis of ligand scaffolds for the basket ligands, the open basket ligands and the PDIpCy ligand. The design of these scaffolds combined a redox-active coordination site alongside an innocent coordination site for the formation of bimetallic complexes. All obtained complexes and their scaffolds have advantages. The most thoroughly examined system is so far the PDIpCy ligand and its complexes as there are structural information for the complexes. A big problem is often the conformation of the coordination of a second metal in our scaffold. The PDIpCy ligand forms homo- and heterobimetallic complexes. A great advantage of this ligand is the two distinct binding sites, which are electronically uncoupled. The synthesised nickel-, zinc- and iron- complexes have to be screened for reactivity. ix List of Abbreviations B magnetic flux density B3LYP Becke, three-parameter, Lee-Yang-Parr – Basis Set for DFT BOC di-tert-butylcarbonate CDCl3 deuterated chloroform cod cyclooctadiene cosy correlation spectroscopy CV cyclic
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