Dicationic Chelating Phosphines – Synthesis, Structure And Reactivity Towards Dienes

by Adam Zielinski
Doctoral thesis
Date of Examination:2021-06-21
Date of issue:2022-06-17
Advisor:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Manuel Alcarazo
Referee:Prof. Dr. Frank Mayer
Persistent Address: http://dx.doi.org/10.53846/goediss-9306

 

 

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Abstract

English

A new family of bidentate dicationic phosphine ligands incorporating an additional electron donating group was designed and synthesized. Obtained ligands were characterized using spectroscopical methods and single crystal diffraction. In comparison with previously established monodentate cationic phosphines, the new ligands allowed to coordinate not only electron rich transition metals such as Au(I) or Pt(II), but also Rh(I) and Ir(I). In order to evaluate the application of new phosphine ligands, the obtained complexes were tested in model reactions. A study of hydroarylation of 1,3 butadiene with electron rich aromatic nucleophiles was performed. Scope and limitation of this reaction was tested, in addition to mechanistic studies. Moreover, obtained Rh(I) complexes were proven to be active catalysts of 2+2+2 Homo Diels-Alder dimerization of norbornadiene derivatives. A family of new norbornadiene dimers was obtained using this methodology. Further mechanistic studies, isolation of reaction intermediates and post-synthetic functionalization were investigated.
Keywords: Phosphine; Dicationic; Ligand; Norbornadiene; Dimerization; Diene hydroarylation; 2+2+2 Homo Diels-Alder
 
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