- 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
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