Bimetallic Complexes for Cooperative Polymerization Catalysis

von Mike Schütze
Dissertation
Datum der mündl. Prüfung:2018-06-25
Erschienen:2018-09-07
Betreuer:Prof. Dr. Franc Meyer
Gutachter:Prof. Dr. Franc Meyer
Gutachter:Prof. Dr. Philipp Vana
Gutachter:Prof. Dr. Marc Walter
Gutachter:Dr. Matthias Otte
Gutachter:Dr. Shoubhik Das
Gutachter:Prof. Dr. Selvan Demir
Zum Verlinken/Zitieren: http://dx.doi.org/10.53846/goediss-7022

 

 

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Englisch

This work contributed to the understanding of cooperativity in bi- and oligometallic complexes through three chapters. The first chapter on CO2/epoxide copolymerization led to the discovery of several promising novel catalysts. One in particular, with an ONO-pincer ligand, provided high polymerization activity and stereoselectivity. The self-assembled ONO-pincer type catalysts proved to be highly active. They serve as proof of concept to the field of CO2/epoxide copolymerization with their new design, coming along with a great potential for future applications, continuing several beneficial features of previously reported catalysts. In the second chapter, the interactions and mutual effects within a dinuclear complex holding an allylpalladium unit and a palladium dihalide unit in close proximity were investigated. New valuable insights into the interactions between the two fragments were gained by changing the substituents and ligands within the complex. The extent of interaction was represented by the allyl exchanges, investigated by kinetic studies through EXSY-NMR spectroscopy. Four model complexes were used for the investigations and to understand the cooperative effects of interest. In the last chapter, a dinuclear nickel complex was investigated for its applicability for the copolymerization of ethylene and MMA. The complex was found to be active for forming the homopolymers PMMA and PE. The complex, after activation with MAO, catalyzes the formation of PMMA with a TOF of 33 1/h (at 23°C) and provided a TOF of up to 19000 1/h (at 25°C and 10 bar ethylene pressure) for PE.
Keywords: cooperativity; catalysis; polymerization; copolymerization; CO2 utilization; CO2 epoxide copolymerization; ONO-pincer; kinetic studies; EXSY-NMR spectroscopy; dinuclear allylpalladium complexes; CCU; CCS; green chemistry; sustainable catalysis; Cooperative Polymerization Catalysis
 
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