Correlations between the Electronic Structure and Energetics of the Catalytic Steps in Homogeneous Water Oxidation Catalysis

[Image: see text] The development of an efficient electrocatalyst for the water oxidation reaction is limited by unfavorable scaling relations between catalytic intermediates, resulting in an overpotential. In contrast to heterogeneous catalysts, the electronic structure of homogeneous catalysts can be modified to a great extent due to a tailored ligand design. However, studies utilizing the tunability of organic ligands have rarely been conducted in a systematic manner and, as of yet, have not produced catalytic paths that avoid the aforementioned unfavorable scaling relations. To investigate the influence of electron-donating groups (EDGs) or electron-withdrawing groups (EWGs) on elementary steps in electrochemical water oxidation catalysis, cis-[Ru(bpy)(2)(H(2)O)](2+) (bpy = 2,2′-bipyridine) was selected as the scaffold that was modified with methyl, methoxy, chloro, and trifluoromethyl groups. This catalyst can undergo several electron transfer (ET), proton transfer (PT), and proton-coupled electron transfer (PCET) steps that were all probed experimentally. In this systematic study, it was found that PCET steps are relatively insensitive with respect to the presence of EDGs or EWGs, while the decoupled ET and PT steps are more heavily affected. However, the influence of the substituents decreases with an increasing oxidation state of Ru due to a lack of d-electrons available at the Ru center for π-backbonding to the bipyridine ligand. Therefore, the Ru(V/VI) redox couple appears to be relatively unaffected by the substituent. Nevertheless, the implementation of EWGs can shift all oxidation events to a very narrow potential window. Not only do our findings illustrate how electronic substituents affect the entire potential energy landscape of the catalytic water oxidation reaction, but they also show that the cis-[Ru(bpy)(2)(H(2)O)](2+) compounds follow different design rules and scaling relations, as has been reported for every other oxygen evolution catalyst thus far.