Introducing Bis(silylene) and Bis(germylene) Pincer Type Ligands in Catalysis vorgelegt von M. Sc. Chemie Daniel Gallego Mahecha aus Bogotá D. C., Kolumbien Von der Fakultät II – Mathematik und Naturwissenschaften der Technischen Universität Berlin Institut für Chemie zur Erlangung des akademischen Grades Doktor der Naturwissenschaften - Dr. rer. nat. - genehmigte Dissertation Promotionsausschuss: Vorsitzender: Prof. Dr. Martin Kaupp (TU Berlin) 1. Gutachter: Prof. Dr. Matthias Driess (TU Berlin) 2. Gutachter: Prof. Dr. Thomas Braun (HU Berlin) Tag der wissenschaftlichen Aussprache: 21-04-2015 Berlin 2015 D83 ii DISSERTATION Introducing Bis(silylene) and Bis(germylene) Pincer Type Ligands in Catalysis by M. Sc. Chemistry Daniel Gallego Mahecha from Bogotá D. C., Colombia iii iv Erklärung Die vorliegende Arbeit entstand in der Zeit von Sep. 2011 bis Mar. 2015 unter der Betreuung von Prof. Dr. Matthias Driess am Institut für Chemie der Technischen Universität Berlin. Von Herzen kommend gilt mein Dank meinem verehrten Lehrer Herrn Professor Dr. Matthias Drieß für die Aufnahme in seinen Arbeitskreis, für seine engagierte Unterstützung, und für die Forschungsfreiheit. v vi To my family, Maria del Mar, Diego, Ariel y Nima, Che, Má y Pá, for being always there despite the distance. “Erfahren, was ist es, ernst genommen zu werden und über das andere zu lachen” “Learn what is to be taken seriously and laugh at the rest” Hermann Hesse “Grau, teurer Freund, ist alle Theorie Und grün des Lebens goldner Baum” “Grey, dear friend, is all theory And green the golden tree of life” Faust I – Mephistopheles Goethe “The beauty of a living thing is not the atoms that go into it, but the way those atoms are put together” Cosmos Carl Sagan vii viii Acknowledgements At the beginning of this PhD, the way looked very long and with plenty of unknown and some scary difficulties. However, thanks to the help of many people this journey has been amenable and enjoyable. First, I would like to thank my supervisor Prof. Dr. Matthias Driess who gave me the possibility to work in this very interesting and challenging project independently. It has been very satisfying to learn about main group and organometallic chemistry under his supervision, I am in debt for his commitment in this field. Secondly, I would like to thank Prof. Dr. Thomas Braun for accepting reviewing this dissertation and be part of the jury committee. I would also want to thank the collaboration partners who have been very important for the successful achievements of my scientific research. I thank Prof. Dr. John F. Hartwig at University of California, Berkeley, who through the Einstein Foundation Fellowship worked during the projects of Iridium and Nickel pincer complexes; for his insightful discussions about catalysis and mechanistic studies, and his commitment in chemistry in general. Also I thank Dr. Andreas Brück who took part as the “catalytic partner” in these two projects from Hartwig’s group, Dankeschön. I feel very thankful with the people who helped for the theoretical calculations for a better and complete understanding of the experiments. I thank Prof. Dr. Martin Kaupp and his co-worker Mr. Florian Meier for their passionate, careful and detailed work about the reaction intermediate of the Sonogashira cross-coupling reaction, Dankeschön. Also I thank Prof. Dr. Shigeyoshi Inoue for his contribution on the calculation of the electronic structure of the iron(0) complexes and for his friendship along this PhD, Arigatou gozaimasu Shige Sensei! And Dr. Tibor Szilvási at the University of Budapest, who appeared just at the right time for calculating the key intermediate of the hydrosilylation of ketones; I am happy that at the end the match theory vs. experiment finalized in a draw, köszönöm szépen Tibi! Finally, I feel gratified with the collaboration with Prof. Dr. Martin Oestreich and his co-worker Toni T. Metsänen during the understanding of the catalytic mechanism of the hydrosilylation of ketones. It was great to see the successful organic-inorganic fusion for a deep understanding in the unexpected mechanism for this system, Dankeschön and Kiitos! ix I am strongly in debt with the people who in one or other way always stayed open for a scientific discussion, suggestion or just to give constant support during the tough days. First, I would like to thank my partner and bro’ Gengwen Tan, it has been really incredible to work with such a passionate and bright chemist. Man, thanks to you this journey was more than simple research but a travel to wonderful and deep understanding of our crazy reactions day by day. I learnt a lot from you not only from chemistry but life as well, Xièxiè wǒ de péngyǒu! I also thank Dr. Burgert Blom, mostly known as Dr. UNO, who became a constant support and a really important guide during my scientific research. Man, I am thoroughly in debt with you for your careful revision of this dissertation. It has been a pleasure to work to your side with our little paws and to laugh as well, despite the stressful moments, Thanks a lot UNO! I am in debt with my mentor at the beginning of my PhD Dr. Wenyuan Wang, who with his patience I got to know the difficulties during this type of chemistry. Also, he taught me that science is an universal language and even when we could not understand each other quite well either in English, German, Chinese, or Spanish, at the end the chemistry knowledge could be transferred without any inconvenient, Xièxiè! My office partners deserve also big thanks because of their constant support, discussions and relaxing chats during the working days. Arindam and Prashant, you both are great, still I have to learn more about Indian cousine and its special and spiiiiiiicy taste! I would also like to thank Nils, who has been a very important friend and support during the last year of the PhD, vielen Dank für deine Unterstützenden Worte mein Freund! Also I am thoroughly in debt with Dr. Stephan Enthaler for his scientific discussions, suggestions and revision of this dissertation, Dankeschön! I also thank all the group members of Metalorganics and Inorganic Materials group under the supervision of Prof. Dr. Matthias Driess, and the groups of Dr. Stephan Enthaler and Prof. Dr. Shigeyoshi Inoue, for their daily support. I especially thank the secretary Andrea Rahmel for all the help in the bureaucratic work during my PhD, Vielen Dank! I also thank all technicians from the Institute für Chemie at the Technische Universität Berlin for their constant help and work. Especially, I would like to thank Paula Nidorf and Dr. Elisabeth Irran for the measuring of single crystals and solving the disordering of the XRD crystallographic structures. Mrs. Christine Klose and Dr. Maria Schlangen for their help x during the mass spectra acquisition of the sensitive metal complexes. And, Samantha Voges and Dr. Jan Dirk Epping for their help during the NMR spectra acquisition. I am thoroughly thankful with the Cluster in Catalysis UniCat in Berlin for giving me the scholarship during my PhD studies. It has been a pleasure to work in such interdisciplinary environment learning from the different fields of catalysis. Also, I thank the graduate school BIG-NSE, in which I took part as fellow, especially to Dr. Jean-Philippe Lonjaret for coordinating the different activities and act as a catalyst for the social meetings with the BIG-NSE students. I thank all my BIG-NSE batch mates who became part of my family in Berlin. Meine liebe crazy Fanni, thanks for all your happiness and football matches either as spectator or player, I am your fan # 1! Mopsi I will always remember your monstrous speed of drinking beer and your flirting skills after the 6th one hahaha. Paddy my rock star and party man, I enjoyed a lot each of your gigs and hic(s)…cops hehehe. Meine liebe katze Laura, happiness and craziness is a perfect mix to being just you, you became like my dear German sister Miaaauuu! Seti, your passion and courage are an inspiration to demand the rights for people for a better world, thanks for keeping this flame alive. Linyu, you and your Chinese wine will always produce me a headache but a nice remembrance of a passionate and involved chemist, Gānbēi! Xunhua, your commitment is an example to follow for a successful career. Matthias, man thanks for showing that theoreticians are not always at the PC but can have an enjoyable way of seeing life. And my shy a pretty Nhan, I really wish to had share more with you but unfortunately chemistry made you disappear, hope you will keep doing great! Also all the other people from different batches, especially the latin mafia Lauris, Maria, Javier, and Ines, it was always nice to have a moment for Spanish refreshment out of all the other languages, gracias ;) This thesis would not have been successful with all the support from the people who always were sending the best energy from the distance. All my university colleagues from the Universidad Nacional de Colombia with their constant support made me possible to represent them with all my best. Especially to Lina, Ingrid, Julio Cesar, Patron, Mikel with their supporting words during the tough times. And my brother and partner Edwin with his humble character of seeing chemistry as a hobby and enjoying every single second of life. xi Pelao, you taught me to be serious at work and laugh at the rest; to be generous with everyone who needs it and being there supporting other ones, even when you are not in the best situation. Hermano, I hope that our dream to create a collaborative research group in organometallic chemistry and homogeneous catalysis, one day will become for real, starting a new wave of research in our adorable country Colombia! I thank deeply from my heart to Andrea, my girlfriend, for being the star in the darkness; for being the balance we all need in love; for her constant support and trust on my capacity not just as chemist but as human being.