Ce-IV- and Light-Driven Water Oxidation by [Ru(terpy)(pic)(3)](2+) Analogues: Catalytic and Mechanistic Studies
2011 (English)In: CHEMSUSCHEM, ISSN 1864-5631, Vol. 4, no 2, 238-244 p.Article in journal (Refereed) Published
A series of mononuclear ruthenium polypyridyl complexes [Ru(Mebimpy)(pic)(3)](PF6)(2) (2; Mebimpy=2,6-bis(1-methylbenzimidazol-2-yl)pyridine; pic=4-picoline), Ru(bimpy)(pic)(3) (3; H(2)bimpy=2,6-bis(benzimidazol-2-yl)pyridine), trans-[Ru(terpy)-(pic)(2)Cl](PF6) (4; terpy=2,2';6',2 ''-terpyridine), and trans-[Ru(terpy)(pic)(2)(OH2)](ClO4)(2) (5) are synthesized and characterized as analogues of the known Ru complex, [Ru(terpy)(pic)(3)](PF6)(2) (1). The effect of the ligands on electronic and catalytic properties is studied and discussed. The negatively charged ligand, bimpy(2-), has a remarkable influence on the electrochemical events due to its strong electron-donating ability. The performance in light- and Ce-IV-driven (Ce-IV=Ce(NH4)(2)(NO3)(6)) water oxidation is successfully demonstrated. We propose that ligand exchange between pic and H2O occurs to form the real catalyst, a Ru-aqua complex. The synthesis and testing of trans[Ru(terpy)(pic)(2)(OH2)](ClO4)(2) (5) confirmed our proposal. In addition, complex 5 possesses the best catalytic activity among these five complexes.
Place, publisher, year, edition, pages
2011. Vol. 4, no 2, 238-244 p.
electrochemistry, homogeneous catalysis, photochemistry, ruthenium, water chemistry
IdentifiersURN: urn:nbn:se:kth:diva-31641DOI: 10.1002/cssc.201000313ISI: 000288043400016ScopusID: 2-s2.0-79951807046OAI: oai:DiVA.org:kth-31641DiVA: diva2:405204
FunderSwedish Research CouncilKnut and Alice Wallenberg Foundation
QC 201103212011-03-212011-03-212011-09-22Bibliographically approved