Change search
ReferencesLink to record
Permanent link

Direct link
Structural Modifications of Mononuclear Ruthenium Complexes: A Combined Experimental and Theoretical Study on the Kinetics of Ruthenium-Catalyzed Water Oxidation
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0003-1662-5817
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
Show others and affiliations
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
Abstract [en]

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.
Keyword [en]
density functional calculations, homogeneous catalysis, N, O ligands, ruthenium, water splitting
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-31388DOI: 10.1002/anie.201005141ISI: 000286729300017ScopusID: 2-s2.0-78650882640OAI: diva2:403705
Swedish Research CouncilKnut and Alice Wallenberg Foundation
QC 20110314Available from: 2011-03-14 Created: 2011-03-14 Last updated: 2012-11-13Bibliographically approved
In thesis
1. Mononuclear Ruthenium Complexes that Catalyze Water to Dioxgen Oxidation
Open this publication in new window or tab >>Mononuclear Ruthenium Complexes that Catalyze Water to Dioxgen Oxidation
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The theme of this thesis is the development of mononuclear Ru-based complexes that are capable of catalyzing the water oxidation (or O2-evolving) reaction, e.g. 2 H2O → O2 + 4 H+ + 4 e. Several families of mononuclear Ru water oxidation catalysts were designed and prepared. They feature with anionic ancillary ligands that contain carboxylate or phenolate donors. The properties of the catalysts were investigated in various aspects including coordination geometry, electrochemical behavior, and ligand exchange. All catalysts showed outstanding catalytic activity towards water oxidation in the presence of cerium(IV) ammonium nitrate as a sacrificial oxidant. High-valent Ru intermediates involved in the reactions were characterized both experimentally and theoretically. The kinetics of catalytic water oxidation was examined based on one catalyst and a prevailing catalytic pathway was proposed. The catalytic cycle involved a sequence of oxidation steps from RuII−OH2 to RuV=O species and O−O bond formation via water-nucleophilic-attack to the RuV=O intermediate. By comparing properties and catalytic performance of Ru catalysts herein with that of previously reported examples, the effect of anionic ancillary ligands was clearly elucidated in the context of catalytic water oxidation. Aiming to further application in an envisaged artificial photosynthesis device, visible light-driven water oxidation was conducted and achieved primarily in a homogeneous three-component system containing catalyst, photosensitizer, and sacrificial electron acceptor. Moreover, one model Ru catalyst was successfully immobilized on ordinary glass carbon surface through a facile and widely applicable method.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 101 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2012:55
Ruthenium complex, Homogeneous catalysis, Water oxidation, O2 evolution, anionic ligand, Molecular catalyst, Electrocatalysis, Kinetics, Artificial photosynthesis, Light-driven, Immobilization of catalyst
National Category
Organic Chemistry Inorganic Chemistry Energy Systems
urn:nbn:se:kth:diva-104765 (URN)978-91-7501-517-0 (ISBN)
Public defence
2012-11-30, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)

QC 20121112

Available from: 2012-11-12 Created: 2012-11-12 Last updated: 2012-11-13Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Tong, LianpengDuan, LeleXu, YunhuaSun, Licheng
By organisation
Organic ChemistryCentre of Molecular Devices, CMD
In the same journal
Angewandte Chemie International Edition
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 46 hits
ReferencesLink to record
Permanent link

Direct link