Mono- and dinuclear ruthenium complexes: synthesis, characterization and their impact in oxidation reactions

Identifier:  TDX:933

Handle: https://hdl.handle.net/20.500.11797/TDX933

Authors:  Röser, Stephan

Abstract:
The main topic of my thesis is the development of new Ruthenium based polypyridyl complexes, with the focus on Ru-aquo compounds. These Ru-aquo compounds present the interesting property of undergoing proton coupled electron processes. This allows such compounds to reach high oxidation states, which is a requirement in redox catalysis. Applications of interest involve the transformation of sulfites into sulfoxides (sulfoxidation) and the oxidation of water to molecular oxygen (water oxidation). At first different mononuclear ruthenium compounds containing one or two DMSO ligands are presented. The obtained findings concerning S- to O-linkage isomerization are transferred and connected to results from catalysis using Ru(H2O)-compounds as catalysts. The second field of interest concerns water oxidation. A variety of mono- and dinuclear Ru(H2O)-compounds differing in electronic and steric properties are described. These differences are connected to the catalytic activity towards water oxidation reaction. New insights in the underlying reaction mechanisms are provided, which constitute a strong basis for the development of future water oxidation catalysts. One highlight of this thesis is the introduction of mononuclear Ru(H2O)-compounds combined with a [Ru(bpy)3]2+ and a CoIII sacrificial electron acceptor, which successfully produce molecular oxygen upon light irradiation. Light driven water oxidation as anode reaction and the recombination of the electrons and protons from the oxidation process at the cathode form a device called solar fuel cell, that once fully mature may play an important role in a future renewable energy system.