Searching for more π-acceptor phosphines: From α-pyridiniophosphines to α-cationic phospholes

by Tim Johannsen
Doctoral thesis
Date of Examination:2022-03-17
Date of issue:2022-04-07
Advisor:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Dietmar Stalke
Referee:Prof. Dr. Johannes C. L. Walker
Referee:Dr. Lisa Vondung
Referee:Dr. Alessandro Bismuto
Referee:Dr. Daniel Janßen-Müller
Persistent Address: http://dx.doi.org/10.53846/goediss-9172

 

 

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Abstract

English

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
 
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