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

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 c...

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Veröffentlicht in:Angewandte Chemie (International ed.) 2011-01, Vol.50 (2), p.445-449
Hauptverfasser: Tong, Lianpeng, Duan, Lele, Xu, Yunhua, Privalov, Timofei, Sun, Licheng
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Sprache:eng
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Zusammenfassung: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.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201005141