Structural Modifications of Mononuclear Ruthenium Complexes: A Combined Experimental and Theoretical Study on the Kinetics of Ruthenium-Catalyzed Water Oxidation
2011 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 50, no 2, 445-449 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2011. Vol. 50, no 2, 445-449 p.
density functional calculations, homogeneous catalysis, N, O ligands, ruthenium, water splitting
IdentifiersURN: urn:nbn:se:kth:diva-31388DOI: 10.1002/anie.201005141ISI: 000286729300017ScopusID: 2-s2.0-78650882640OAI: oai:DiVA.org:kth-31388DiVA: diva2:403705
FunderSwedish Research CouncilKnut and Alice Wallenberg Foundation
QC 201103142011-03-142011-03-142012-11-13Bibliographically approved