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To design the ideal water oxidation catalyst, understanding of the catalytic mechanism and decomposition pathways is essential. The aim of the research described in this thesis is to provide mechanistic insight on the water oxidation reaction catalyzed by homogeneous electrocatalysts and topostulate design criteria for the ideal water oxidation catalyst.

In this dissertation, the synthesis and characterization of a series of iron complexes based on different ligand platforms are described. The complexes are subsequently studied for their activity in catalytic water oxidation with the help of a variety of electroanalytical techniques. The results show that the catalytic activity of structurally related iron complexes correlates strongly with the electronics of the iron centre. Another potentially very important aspect in the field of homogeneous electrocatalysis which has so far received only very little attention in published literature is the influence of the nature of the electrode material on the resulting electrochemistry. The results discussed in thesis show that interactions between the working electrode and the catalyst in solution can exhibit a strong influence on the resulting electrochemistry. Overall, the results of this work demonstrate that iron-based complexes can indeed be made to work as electrocatalysts for the water oxidation reaction. Furthermore, the results show that the electronic structure of the iron centre is a promising target for the design of new and improved catalysts. Finally, the results also highlight the importance of trying out different electrode materials as part of routine tests of new potential electrocatalysts.