Constitution and Reactivity of Palladium Ate Complexes in Cross-Coupling Reactions
von Marlene Kolter
Datum der mündl. Prüfung:2019-09-24
Erschienen:2020-02-18
Betreuer:Prof. Dr. Konrad Koszinowski
Gutachter:Prof. Dr. Konrad Koszinowski
Gutachter:Prof. Dr. Lutz Ackermann
Dateien
Name:Marlene_Kolter_Dissertation.pdf
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Zusammenfassung
Englisch
Palladium-catalyzed cross-coupling reactions are among the most widely used tools for the formation of new carbon-carbon or carbon-heteroatom bonds in organic synthesis. Usually, the intermediates involved in the catalytic cycle are described as neutral palladium complexes. In some cases, however, anionic palladium species have been suggested as important reaction intermediates. In the course of this work, different kinds of anionic palladium complexes were thoroughly characterized regarding their formation, structure, and reactivity, using electrospray ionization mass spectrometry and gas-phase reactions as the main analytical methods along with NMR spectroscopy, electrical conductivity measurements, and UV/Vis spectroscopy. These studies allowed not only the identification of previously proposed anionic reaction intermediates, but also the detection of other potentially reactive anionic species along with catalyst decomposition products and aggregates. Thus, the results presented in this work provide a deeper insight into the role of palladate intermediates in several variants of cross-coupling reactions at different stages of the catalytic cycle.
Keywords: Palladium; Pd(0); Pd(II); Catalysis; Cross-Coupling Reactions; Reactive Intermediates; Gas-Phase Chemistry; Palladate Complexes; ESI Mass Spectrometry