Structural Modifications of Mononuclear Ruthenium Complexes:  A Combined Experimental and Theoretical Study on the Kinetics of Ruthenium‐Catalyzed Water Oxidation

Abstract

Small change, big difference: A minor structural modification of water-oxidation catalysts changes the kinetics of O2 evolution from second- to first-order (see scheme). According to DFT calculations, the torsional flexibility of the chelating ligands and their reorganization through the catalytic cycle are implicated in pathway selectivity, and the auxiliary carboxylate group becomes involved in proton-coupled nucleophilic attack. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.