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Dokumentvorlage Für Wissenschaftliche Arbeiten Synthesis of Novel Homoleptic and Heteroleptic Transition Metal Carbonyl and Nitrosyl Cations INAUGURALDISSERTATION zur Erlangung des Grades eines Doktor der Naturwissenschaften (Dr. rer. nat.) der Fakultät für Chemie und Pharmazie der Albert-Ludwigs-Universität Freiburg im Breisgau vorgelegt von Jan Bohnenberger aus Saarlouis 2020 Selbstständigkeitserklärung Die vorliegende Arbeit wurde in der Zeit von 15.06.2016 bis 10.03.2020 am Institut für Anorganische und Analytische Chemie der Albert-Ludwigs-Universität unter der Leitung von Herrn Prof. Dr. Ingo Krossing angefertigt. Vorsitzender des Promotionsausschusses: Prof. Dr. Stefan Weber Dekan: Prof. Dr. Oliver Einsle Referent: Prof. Dr. Ingo. Krossing Korreferent: Prof. Dr. Philipp Kurz Datum der mündlichen Prüfung: 04.05.2020 “Sometimes science is more art than science, Morty. A lot of people don't get that.” — Rick Sanchez, Rick And Morty Danksagung Mein erster und grundsätzlicher Dank gilt Prof. Ingo Krossing, zuallererst natürlich für die Möglichkeit, meine Doktorarbeit in seinem Arbeitskreis anfertigen zu dürfen. Darüber hinaus bedanke ich mich herzlich bei ihm für die tolle Betreuung, die vielen fruchtbaren Gespräche und die Möglichkeit, mich weitestgehend frei in der ‚molekularen Spielwiese‘ meines Dissertationsthemas austoben zu dürfen. Prof. Philipp Kurz danke ich für die Übernahme des Korreferats, sowie Prof. Thorsten Koslowski für seine Bereitschaft mich zu prüfen. Ich bedanke mich auch bei: Meinen ehemaligen Mitarbeiterpraktikanten Manuel Schmitt und Brandon Derstine sowie bei meinem Bachelorand Richard Kopp – und wünsche Ihnen das Beste für ihre zukünftigen Wege. Meinen (teilweise ehemaligen) Labormitbewohnern Wiebke Unkrig, Stefan Meier, Philippe Weis und Manuel Schmitt für Diskussion, Freude, Ärger, Dampfablassen, Problemlösen, Hilfestellungen und und und. Danke für die tolle Atmosphäre, ohne mich dürft ihr bald endlich Musik hören! Allen Leuten, die mir fachlich bei Fragen zur Seite gestanden haben: Dr. Daniel Himmel, Manuel Schmitt und Dr. Burkhard Butschke beim Thema DFT Rechnungen; Dr. Daniel Kratzert bei Kristallstrukturen; Dr. Harald Scherer, dem NMR Guru; Dr. Michael Daub und Dr. Thilo Ludwig bei Fragen zu Pulver-XRDs und natürlich dem Subgroup-Meeting zur Diskussion aller aufgekommenen Probleme und darüber hinaus. Wolfram Feuerstein und Prof. Frank Breher für die zwei tollen Kooperationen. Dem gesamten AK Krossing natürlich. Dr. Thilo Ludwig für sein mustergültiges ‚Chefsein‘ bei der AGP Betreuung. Dr. Harald Scherer und Fadime Bitgül für das Messen von NMR Spektren, Dr. Thilo Ludwig und Dr. Michael Daub für das Messen von Pulver-XRDs. Brigitte Breitling, Vera Brucksch und Franziska Harder, den drei Schutzpatroninnen aus der Verwaltung. Danke für Kopien und Scans, Hilfe bei dummen Fragen, Hilfe bei dümmeren Fragen und Hilfe bei noch dümmeren Fragen. Ohne euch stünde alles Kopf! Winfried Weber, Tim Lecke sowie der gesamten Werkstatt für ihre Versorgung mit Gasflaschen, Glasgeräten und der schnellen Abwicklung diverser Aufträge. Der kleinen Glovebox, weil sie relativ wenig Probleme gemacht hat. Meinem Stehschreibtisch. Explizit nicht danken möchte ich Bandscheibenvorfällen. Dem Bierclub („Schon mal aus dem Fenster geschaut?“). Dr. Burkhard Butschke für Gespräche über Gott und die Welt und süchtig machende Halva-Fäden. Michael Langenmaier und Nils Pompe für das Zusammenhalten der Mensa-Gang. Trotz unregelmäßiger Ditchungen. Der gesamten (Ex-)Freiburg Crew. Es war und ist eine geile Zeit. Meiner Familie für die grundsätzliche Unterstützung und das geduldige Zuhören bei den ewigen Monologen beim möglichst anschaulichen Erklären meiner Forschung. Und meiner Oma Alice, die leider von uns gegangen ist und nicht mehr die Verleihung meines Doktortitels mitbekommen konnte – du wärst sicherlich stolz auf mich, wie schon immer. Last but not least geht mein Dank an meine Partnerin Hien Tran für unsere wunderbare gemeinsame Zeit. Teile dieser Arbeit basieren auf den bereits veröffentlichten oder akzeptierten Publikationen: Kapitel 3: “Stable Salts of the Hexacarbonyl Chromium(I) Cation and its Pentacarbonyl- Nitrosyl Chromium(I) Analogue” von Jan Bohnenberger, Wolfram Feuerstein, Daniel Himmel, Michael Daub, Frank Breher und Ingo Krossing, Nat. Commun. 2019, 10, 624.” (DOI: 10.1038/s41467-019-08517-2). Dieser Artikel ist online frei verfübar. Kapitel 4: “Completing the Triad: Synthesis and full Characterization of Homoleptic and Heteroleptic Carbonyl and Nitrosyl Complexes of the Group VI Metals” von Jan Bohnenberger, Manuel Schmitt, Wolfram Feuerstein, Ivo Krummenacher, Burkhard Butschke, M. Jakub Czajka, Przemysław J. Malinowski, Frank Breher und Ingo Krossing, Chem. Sci. 2020, accepted article (DOI: 10.1039/C9SC06445A). Kapitel 5: “Stable Salts of Heteroleptic Iron Carbonyl/Nitrosyl Cations – A New Class of Iron Carbonyl Complexes” von Jan Bohnenberger und Ingo Krossing, Angew. Chem. Int. Ed. 2020, 59, 1–6, early view (DOI: 10.1002/anie.201915942) mit Erlaubnis von John Wiley and Sons. Copyright © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Die deutsche Version ist unter DOI: 10.1002/ange.201915942 zugänglich. Kapitel 6: “Going Homoleptic: Synthesis and Full Characterization of Stable Manganese Tetranitrosyl Cation Salts” von Jan Bohnenberger, Brandon Derstine, Michael Daub und Ingo Krossing, Angew. Chem. Int. Ed. 2019, 58, 9586–9589” (DOI: 10.1002/anie.201904191) mit Erlaubnis von John Wiley and Sons. Copyright © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Die deutsche Version ist unter DOI: 10.1002/ange.201904191 zugänglich. Die Manuskripte der o.g. Publikationen sind Bestandteil einzelner Kapitel in dieser Arbeit einschließlich der elektronischen Zusatzinformationen („Electronic Supporting/Supplementary Information“, ESI oder S.I.). Hierfür wurden die notwendigen Genehmigungen, d.h. die vollständige (inkl. Übersetzung) Verwendung der Publikationen in einer Dissertation in gedruckter und digitaler Form, bei dem Verlag John Wiley and Sons eingeholt; der Verlag RSC Publishing verlangt keine ausdrückliche Genehmigung für diese Nutzung in der eigenen Thesis. Aus Gründen eines einheitlichen Layouts wurden wenige Formatierungen, wie eine Anpassung der Nummerierung sowie der Verweise auf die S.I. vorgenommen, um eine bessere Übersichtlichkeit zu gewährleisten. Sämtliche Daten, die Basis dieser Publikationen sind, sind in den jeweiligen Supporting Information Dateien online kostenfrei abrufbar. Zusammenfassung I Zusammenfassung Das Ziel dieser Arbeit war die Synthese neuartiger Übergangsmetallkomplexkationen, die durch schwach koordinierende Anionen (engl. WCAs) stabilisiert wurden. Als Übergangsmetalle wurden die Metalle Cr, Mn und Fe der 3d-Reihe, sowie die homologe Triade der Gruppe VI Cr, Mo und W verwendet und untersucht. Als Liganden wurden die Gasmoleküle Kohlenstoffmonoxid (CO) und Stickstoffmonoxid (NO) verwendet. Alle erhaltenen Komplexe der Art [M(CO)x(NO)y][WCA] (x = 0– F – F – 6, y = 4–0; M: Cr, Mo, W, Mn, Fe; WCA = [Al(OR )4] , [F-{Al(OR )3}2] ) wurden vollständig mittels Schwingungsspektroskopie, NMR- oder EPR- Spektroskopie und Einkristall- und Pulverdiffraktometrie charakterisiert, sowie die gemessenen Daten durch quantenmechanische Rechnungen unterstützt und bestätigt. Homoleptische Übergangsmetallcarbonylkomplexe sind seit über 130 Jahren bekannt. Mittlerweile kennt diese Verbindungsklasse zahlreiche Vertreter, die oftmals dank ihrer reichhaltigen Folge-, Redox- und Substitutionschemie umfassend untersucht wurden. Allerdings ist die Familie der Carbonylkationen aufgrund ihrer intrinsisch hohen Reaktivität deutlich unterrepräsentiert und radikalische Spezies sowie kationische Clusterverbindungen waren bis dato völlig unbekannt. Im Rahmen dieser Arbeit gelang es erstmals, stabile WCA-Salze der homologen Reihe der radikalischen + Übergangsmetallcarbonylkomplexkationen [Cr/Mo/W(CO)6] als WCA-Salze zu synthetisieren und vollständig zu charakterisieren. Homoleptische Übergangsmetallnitrosylkomplexe sind generell deutlich rarer als ihre Carbonyl- analoga. Nur je ein anionischer und neutraler homoleptischer Vertreter konnte bisher isoliert und charakterisiert werden, Kationen waren gänzlich unbekannt. Im Laufe dieser Arbeit konnte das + erste homoleptische Übergangsmetallnitrosylkation [Mn(NO)4] als WCA-Salz synthetisiert und umfassend untersucht werden. Gerade in Hinblick auf die komplexe Bindungssituation des NO Liganden konnten dadurch neue Erkenntnisse gewonnen werden. Gemischte, heteroleptische, Carbonyl/Nitrosylkomplexkationen sind, vergleichbar zu ihren homoleptischen Artverwandten, ähnlich unerforscht gewesen: Nur ein einziger Komplex dieser Spezies wurde bislang beobachtet. Als Teil dieser Arbeit konnten die WCA-Salze der neuen Spezies + + + [Cr/Mo/W(CO)5(NO)] , [Fe(CO)4(NO)] und [Fe(CO)(NO)3] synthetisiert und vollständig charakterisiert werden. II Abstract Abstract The aim of this thesis was the synthesis of novel and unprecedented transition metal cations, stabilized by weakly coordinating anions (WCAs). For that, the 3d transition metals Cr, Mn, Fe and the group VI triad Cr, Mo and W were examined in combination with the gas molecules carbon monoxide (CO) and nitrogen monoxide (NO) as ligands. The obtained complexes in the fashion F – F – [M(CO)x(NO)y][WCA] (x = 0–6, y = 4–0; M: Cr, Mo, W, Mn, Fe; WCA = [Al(OR )4] , [F-{Al(OR )3}2] ) were fully characterized by vibrational spectroscopy, NMR or EPR spectroscopy as well as single- crystal and powder X-ray diffraction. The obtained data were supported and validated by quantum mechanical
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