Journal article
Water oxidation catalysis with ligand substituted Ru-bpp type complexes
Catalysis science & technology, Vol.6(13), pp.5088-5101
01/01/2016
DOI: 10.1039/c6cy00197a
Abstract
A series of symmetric and non-symmetric dinuclear Ru complexes of general formula {[RuR(2)trpy)H2O)][Ru(R-3-trpy)(H2O)](mu-R-1-bpp)}(3+) where trpy is 2,2':6',2 ''-terpyridine, bpp(-) is 3,5-bis(2-pyridyl)pyrazolate and R-1, R-2 and R-3 are electron donating (ED) and electron withdrawing (EW) groups such as Me, MeO, NH2 and NO2 have been prepared using microwave assisted techniques. These complexes have been thoroughly characterized by means of analytical (elemental analysis), spectroscopic (UV-vis, NMR) and electrochemical (CV, SQWV, CPE) techniques. The single crystal X-ray structures for one acetate-and one chloro-bridged precursor have also been solved. Kinetic analysis monitored by UV-vis spectroscopy reveals the electronic effects exerted by the ED and EW groups on the substitution kinetics and stoichiometric water oxidation reaction. The catalytic water oxidation activity is evaluated by means of chemically (Ce-IV), electrochemically, and photochemically induced processes. It is found that, in general, ED groups do not strongly affect the catalytic rates whereas EW groups drastically reduce catalytic rates. Finally, DFT calculations provide a general and experimentally consistent view of the different water oxidation pathways that can operate in the water oxidation reactions catalyzed by these complexes.
Details
- Title: Subtitle
- Water oxidation catalysis with ligand substituted Ru-bpp type complexes
- Creators
- Stephan Roeser - Institut Català d'Investigació QuímicaFernando Bozoglian - Institut Català d'Investigació QuímicaCraig J. Richmond - Institut Català d'Investigació QuímicaAaron B. League - University of MinnesotaMehmed Z. Ertem - University of MinnesotaLaia Francas - Institut Català d'Investigació QuímicaPere Miro - University of MinnesotaJordi Benet-Buchholz - Barcelona Inst Sci & Technol, Inst Chem Res Catalonia ICIQ, Ave Paisos Catalans 16, E-13007 Tarragona, SpainChristopher J. Cramer - University of MinnesotaAntoni Llobet - Institut Català d'Investigació Química
- Resource Type
- Journal article
- Publication Details
- Catalysis science & technology, Vol.6(13), pp.5088-5101
- Publisher
- Royal Soc Chemistry
- DOI
- 10.1039/c6cy00197a
- ISSN
- 2044-4753
- eISSN
- 2044-4761
- Number of pages
- 14
- Grant note
- 1361595 / Division Of Chemistry; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) "La Caixa" foundation; La Caixa Foundation CTQ-2013-49075-R; SEV-2013-0319; CTQ-2014-52974-REDC; ENE2014-52280-REDT / MINECO; Spanish Government
- Language
- English
- Date published
- 01/01/2016
- Academic Unit
- Chemistry
- Record Identifier
- 9984618512202771
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