Transition metal catalysis in confined spaces

Chemical reactions are required for the conversion of feedstocks to valuable materials, such as different types of plastics, pharmaceutical ingredients and advanced materials. In order to facilitate the conversion of these feedstocks to a wide array of products, catalysis plays a prominent role. Catalysts, being able to facilitate shortcuts in the conversion of materials, make reactions more atom‐economical and prevent the formation of waste. This makes catalysis an important field in chemistry and allows it to contribute to society by acquiring products in a sustainable way. However, the development of catalysts that display high reactivity and selectivity is not straightforward and new methodologies and catalysts are required to sustain and extend our high standard of living. In order to influence the selectivity in catalysis, the environment around the active site or active species can be changed. While traditional methods change the first coordination sphere around the catalyst by modification of the ligand, new methods in which a second coordination sphere is generated around the active site are arising. This thesis describes the formation of a second coordination around metal catalysts via supramolecular assembly. By combining ditopic building blocks (L) with a metal precursor (M) large molecular spheres of the type M12L24 are formed in which 24 metal complexes are embedded. The formed spheres are explored in catalysis and result in new selectivity and reactivity compared to the mono‐nuclear catalyst.