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From Intermetallics to Intermetalloid Clusters Molecular Alloying of Aluminum and Gallium with Transition Metals

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Technische Universität München Lehrstuhl für Anorganische und Metallorganische Chemie From Intermetallics to Intermetalloid Clusters Molecular Alloying of Aluminum and Gallium with Transition Metals Jana Weßing Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.) genehmigten Dissertation. Vorsitzender: Prof. Dr. Thomas F. Fässler Prüfende der Dissertation: 1. Prof. Dr. Roland A. Fischer 2. Prof. Dr. Jean-Yves Saillard 3. Prof. Dr. Stefanie Dehnen Die Dissertation wurde am 01.03.2018 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 30.04.2018 angenommen. FROM INTERMETALLICS TO INTERMETALLOID CLUSTERS Molecular Alloying of Aluminum and Gallium with Transition Metals Dissertation Jana Weßing Die vorliegende Arbeit wurde am Lehrstuhl für Anorganische Chemie II der Ruhr- Universität Bochum im Zeitraum von Januar 2014 bis März 2016, sowie am Lehrstuhl für Anorganische und Metallorganische Chemie der Technischen Universität München im Zeitraum von April 2016 bis März 2018 erstellt. Danksagung In erster Linie gilt mein besonderer Dank Prof. Dr. rer. nat. Dr. phil. h.c. Roland A. Fischer für die Möglichkeit mich in den letzten Jahren in Ihrer fachlich, wie menschlich herausragenden Arbeitsgruppe verwirklichen zu können. Ihnen verdanke ich nicht nur ein faszinierendes wissenschaftliches Thema, das meine Aufmerksamkeit trotz diverser Tiefschläge im Labor wecken und kontinuierlich fesseln konnte, sondern vor Allem die Gelegenheit alte Strukturen zu verlassen und mich in allen Belangen an neuen Herausforderungen messen und weiterentwickeln zu können. Für Ihr mir dabei entgegengebrachtes Vertrauen und Ihre Unterstützung bin ich von Herzen dankbar. Meiner Prüfungskommission danke ich für die bereitwillige und freundliche Übernahme des Koreferats. Wie so oft haben auch an der Entstehung dieser Arbeit zahlreiche Menschen, bewusst oder unbewusst, mitgewirkt, deren Name nicht auf dem Deckblatt stehen. Ihnen allen gebührt an dieser Stelle ein großes DANKESCHÖN. Insbesondere möchte ich mich bedanken bei... / I am particularly thankful to... ... Dr. Christian Gemel für seine stets offene Tür bei wissenschaftlichen Fragestellung aller Art, sowie seinen Enthusiasmus und die Kreativität in der Herangehensweise an eben diese. ... Dr. Mariusz Molon und Dr. Ganesamoorthy Chelladurai, dafür mein Interesse an der Organometallchemie nicht geweckt, aber befeuert zu haben und mir den Einstieg in die OM- Gruppe, sowie mein spannendes Promotionsthema geebnet zu haben. ... Prof. Dr. Jean-Yves Saillard, Dr. Samia Kahlal and Dr. Rémi Marchal for the quantum chemical calculations on [Cu43(AlCp*)12] which finally round the topic off, and greatly contributed to this great chapter. ... Prof. Olivier Cador and Prof. Birgit Weber, as well as Christoph Göbel for magnetic susceptibility measurements. ... Dr. Rüdiger Seidl und Dr. Alexander Pöthig, sowie den "Pöthig Boys" Philipp Altmann und Christian Jandl für die Unterstützung bei kleineren und größeren kristallographischen Problemfällen, insbesondere jedoch für die Vertiefung meiner ursprünglich doch recht rudimentären Kristallographiekenntnisse. ... Dr. Gabriele Raudaschl-Sieber für das Ermöglichen teils recht kurzfristiger Festkörper-NMR-spektroskopischer Messungen und ihr Engagement insbesondere bei schwierigen Proben. ... Julius Hornung für quantenchemische Rechnungen und LIFDI-MS Messungen. ... Tim Kratky für abenteuerliche XPS Messungen unter Luftausschluss und die hilfsbereite Unterstützung bei deren Interpretation. ... den Bochumer und Münchener "Office Ladies" Sabine Pankau, Jacinta Essling, Gabriele Querbach und Martin Schellerer. Ohne eure stete Ansprechbarkeit sowie Unterstützung in allen administrativen Dingen wäre der Uni-Alltag bedeutend aufreibender. Danke dass ihr, viel zu oft unbemerkt, dafür sorgt, dass alles läuft. ... den hilfsbereiten Technikern und Angestellten von RUB und TUM, Uschi Herrmann, Martin Gartmann, Jürgen Kudermann, Maria Weindl, Peter Richter, Tobias Kubo, Rodica Dumitrescu, Ulrike Ammari, Petra Ankenbauer, Bircan Dilki und Carmen Hessner, für ihre tatkräftige Unterstützung im (Labor-)Alltag und bei den Analysen. ... den Studenten, die ich im Rahmen von Forschungspraktika oder Abschlussarbeiten begleiten durfte: Niklas Cibura, Patrick Wonner, Maximilian Göckeler, Cindy Beyer, Okan Yildirim, Jonas Bruckmoser, Alexander Engel und Christian Jakob. Ganz besonderer Dank gebührt Lena Staiger für ihren Einsatz in der Masterarbeit und natürlich die weltbeste Ni(cdt) Synthese. ... dem Fonds der Chemischen Industrie und der Gesellschaft Deutscher Chemiker für die finanzielle Unterstützung in Form eines Promotionsstipendiums und Reisebeihilfe. Abseits von allem Organisatorischem und Fachlichem ist doch das Menschliche ausschlaggebend für den Spaß an der Arbeit. Daher möchte ich von ganzem Herzen den lieben Menschen danken, die das Leben in und außerhalb des Laboralltags so lebenswert gemacht haben, mit denen ich kleine Erfolge feiern und große Misserfolge schönreden (oder unter den Tisch trinken) konnte, oder die Uni auch mal ganz vergessen durfte. Daher danke ich meinen Kollegen der jetzigen AMC, insbesondere Alexander Pöthig, Philipp Altmann, Suttipong Wannapiboon, David Mayer, Anna-Lisa Semrau, Konstantin Epp, Julius Hornung, Lena Staiger, Kathrin Kratzl und Pia Vervoorts für eine großartige, teils ausgelassene Gruppenatmosphäre, den Zusammenhalt und diverse gemeinsame Aktivitäten in und außerhalb der Uni. Unserer OM-Gruppen "Mutti" Kerstin Freitag möchte ich für das Auffangen nach dem Umzug nach München danken, und für die geteilte Leidenschaft für schweißtreibende Wandertouren. Den Mitgliedern der MolKat Arbeitsgruppe bin ich außerdem dankbar für die herzliche Aufnahme an der TUM. Mein herzlicher Dank gilt weiterhin meinen Bochumer Leidensgenossen der ehemaligen ACII, vor Allem aber weiten Teilen von Anjanas Kindergarten: Alexander Sadlo, Stefan Cwik, Sarah Karle, Richard O'Donoghue, Jiyeon Kim und Daniel Peeters für die gemeinsamen Kaffeepausen, die endlosen Abende im Bermudadreieck und Feierabendbier "vor vier". Jiyeon Kim und Andreas Schneemann bin ich dankbar für den "awesome roadtrip" durch Kanada und die USA im Anschluss an das ACS Fall Meeting 2015. Clarissa Kroll und Jiyeon Kim bin ich zudem dankbar für Korean BBQ und leider viel zu seltene "Girls Days". Olesia Halbherr, unserer ewigen Kaffeekönigin, danke ich von Herzen für ihre Freundschaft auch außerhalb der Uni, insbesondere für die vielen Gespräche bei literweise Kaffee, die gemeinsamen Spieleabende und dafür, dass du mich an deiner kleinen Familie teilhaben lässt. Furthermore, I am thankful to Marissa Kerrigan, whom I know "live" for just a couple of weeks, for her decision to cross the Atlantic for a research stay with the CVD group, and the resulting honest friendship. Meinen Geschwistern Dennis, Fabian und Benjamin und meinen Eltern Beate und Karsten Weßing danke ich von Herzen für die liebevolle Unterstützung in den letzten Jahren, das aufgebrachte Verständnis in jeder Lebenssituation, das Auffangen in etwaigen kleineren und größeren Krisen und das hartnäckige Nachbohren, wann ich denn mal langsam fertig werde. Daran, dass es jetzt endlich soweit ist habt ihr einen wesentlichen Anteil! Zu guter Letzt gilt mein zutiefster Dank Daniel Peeters. Ich kann wohl kaum in Worte fassen, wie unendlich dankbar ich dir bin, für deine großartige Unterstützung, deine unerschütterliche Gelassenheit und deine Fähigkeit mir immer wieder das Wesentliche vor Augen zu führen, vor Allem aber für deinen Humor und die kostbare gemeinsame Zeit. Ohne deinen Rückhalt in und außerhalb der Uni, die Aufmunterung an rabenschwarzen Tagen und dein uneingeschränktes Verständnis gerade in der letzten Zeit wäre diese Arbeit vermutlich nie so weit gekommen. “Curiosity is a descending stair… that leads to only who-knows-where.” ― Jasper Fforde I Table of contents I Table of contents I Table of contents ............................................................................................................. i II List of figures ................................................................................................................ iv III List of schemes ............................................................................................................ viii IV List of tables .................................................................................................................. ix V List of abbreviations ....................................................................................................... x 1 MOTIVATION ...................................................................................................................... 1 2 SUMMARY........................................................................................................................... 4 3 INTERMETALLIC PHASES AND CLUSTERS ............................................................... 12 1.1 Intermetallic phases ...................................................................................................... 13 1.2 Top-Down! From solid-state phases to molecular clusters .......................................... 29 1.3 Metal cluster compounds .............................................................................................. 32 1.4 Bottom-up! From a molecular view to the solid state .................................................. 51 1.5 Hume-Rothery phase
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  • Appendix 7 Tanabe-Sugano Diagrams and Some Illustrative Spectra

    Appendix 7 Tanabe-Sugano Diagrams and Some Illustrative Spectra

    Appendix Consider the ligand ethylenediamine, en, which is typical of many. When it chelates to a metal atom a five-membered ring is formed, as shown in Fig. A 1.1. Is this ring planar? The answer is no, it is puckered. It is easy to see why this should be so. In a regular pentagon each internal angle is 108°, not far from the regular tetrahedron value of 109.SO. However, if the chelate ring is part of an octahedral complex then the N- M- N angle will be close to 900. This will open up the bond angles at the four atoms of the en ligand in the ring to an average of 112.5°; add to this the fact that the M- N bonds will be longer than the C--C and C- N and it is clear that some steric strain is likely to exist. This strain can be relieved at little or no cost if the ring puckers. Having recognized the possibility of puckering, the next thing is to recognize that two different puckered forms exist; much of this appendix is concerned with them. Any three points in space define a plane, unless the three points lie in a straight line. Consider the plane defined by the metal atom and the two nitrogen atoms of an en ligand in a complex. Our concern is with the two carbon atoms in the ligand. Relative to the plane, these can be arranged in either of the two ways shown in the top part of Figure A1.2.