Searching for more π-acceptor phosphines: From α-pyridiniophosphines to α-cationic phospholes
von Tim Johannsen
Datum der mündl. Prüfung:2022-03-17
Erschienen:2022-04-07
Betreuer:Prof. Dr. Manuel Alcarazo
Gutachter:Prof. Dr. Manuel Alcarazo
Gutachter:Prof. Dr. Dietmar Stalke
Gutachter:Prof. Dr. Johannes Jun.-Walker
Gutachter:Dr. Lisa Vondung
Gutachter:Dr. Alessandro Bismuto
Gutachter:Dr. Daniel Janßen-Müller
Dateien
Name:PhD_Thesis_Tim_Johannsen.pdf
Size:13.8Mb
Format:PDF
Zusammenfassung
Englisch
This thesis focuses on two classes of cationic phosphines. In the first part, the previously developed cationic pyridinio-phosphines were investigated further in respect to their coordination chemistry towards Ir and their applications in pi-acid catalysis. In the second and major part, a new class of cationic phosphines, the cationic phospholes are introduced. The cationic phospholes were prepared in a concise and scalable synthesis. With four different cationic phospholes in hand, their electronic properties were investigated by means of IR-spectrometry, P-NMR of Se-adducts and cyclic/squarewave voltammetry. Their structural characteristics could be shown by X-ray analysis and buried volume calculations. The reactivity of the prepared compounds in oxidations and Diels-Alder reactions could be shown, as well as their coordination chemistry towards Au(I). From the synthesized Au-complexes, three were tested in catalysis, where they showed high reactivity and selectivity in the tested hydroarylation- and cyclisation-reactions.
Keywords: cationic phosphines; cationic phospholes; phospholes; pi-acid catalysis; gold catalysis