- Proton-responsive pyridine-based ligands: Synthesis, coordination chemistry and catalysis
- Award date
- 28 June 2016
- Number of pages
- Document type
- PhD thesis
- Faculty of Science (FNWI)
- Van 't Hoff Institute for Molecular Sciences (HIMS)
Catalysts are in dispensable for society as they are applied in the majority of industrial processes. Catalysts can increase the rate at which a reaction proceeds, but can also selectively produce only one product, thereby preventing side reactions and the production of side products or waste, resulting in more efficient, atom-economical and environmentally benign processes. In homogeneous catalysis, the catalyst often consists of a transition metal that is surrounded by ligands. Reactive or proton-responsive ligands may be envisioned to operate in a synergistic way with the metal to facilitate a chemical process. This concept of metal-ligand cooperation (MLC) has gained a lot of interest over the past decade and is currently a rapidly expanding field of homogeneous catalysis.
The research described in this thesis is focused on the development of new metal complexes bearing different proton-responsive ligand systems. More specifically, several bidentate and tridentate types of pyridine-based ligands are described, based on phosphinomethylpyridines, pyridones and pyrazoles. They all exhibit a cooperative character in their own specific way. The coordination to mainly 2nd row late-transition metals (Ru, Rh, and Pd) is successfully demonstrated, along with the behavior of their bifunctional character. Application in several catalytic transformations is studied, including various dehydrogenative coupling reactions and the intramolecular hydroamination of aminoalkenes and -alkynes.
- Research conducted at: Universiteit van Amsterdam
Thesis (complete) (Embargo up to and including 18 June 2018)
Chapter 3: Ruthenium PNN(O) complexes: Cooperative reactivity and application as catalysts for acceptorless dehydrogenative coupling reactions (Embargo up to and including 18 June 2018)
Chapter 4: The reactivity of Rh(I) and Pd(II) complexes with multi-site cooperative PNN(O) pincer ligands (Embargo up to and including 18 June 2018)
Chapter 5: Complexes based on tridentate NNN pincer ligands: Reactivity and application in catalysis (Embargo up to and including 18 June 2018)
If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library, or send a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible.