Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand
2010 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, no 15, 4659-4668 p.Article in journal (Refereed) Published
Two mononuclear ruthenium complexes [RuL(pic)(3)] (1) and [RuL(bpy)(pic)] (2) (H2L = 2,6-pyridinedicarboxylic acid, pic=4-picoline, bpy = 2,2'-bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium-based water oxidation catalysts using [Ce(NH4)(2)(NO3)(6)] (Ce-IV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnovers(-1). Under acidic conditions, the equatorial 4-picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the Rum state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using Ce-IV as oxidant, [RuL(pic)(2)(H2O)](+) is proposed as the real water oxidation catalyst.
Place, publisher, year, edition, pages
2010. Vol. 16, no 15, 4659-4668 p.
electrochemistry, homogeneous catalysis, oxidation, ruthenium, water splitting
IdentifiersURN: urn:nbn:se:kth:diva-27911DOI: 10.1002/chem.200902603ISI: 000277331000027ScopusID: 2-s2.0-77950824222OAI: oai:DiVA.org:kth-27911DiVA: diva2:383045
QC 201101042011-01-042011-01-032011-09-22Bibliographically approved