Catalytic Water Oxidation by Mononuclear Ru Complexes with an Anionic Ancillary Ligand
| العنوان: | Catalytic Water Oxidation by Mononuclear Ru Complexes with an Anionic Ancillary Ligand |
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| المؤلفون: | Lele Duan, A. Ken Inge, Xiaodong Zou, Lei Wang, Licheng Sun, Lianpeng Tong |
| المصدر: | Inorganic Chemistry. 52:2505-2518 |
| بيانات النشر: | American Chemical Society (ACS), 2013. |
| سنة النشر: | 2013 |
| مصطلحات موضوعية: | Anions, Models, Molecular, Ligand, Chemistry, Molecular Conformation, Water, Electrochemical Techniques, Crystallography, X-Ray, Ligands, Combinatorial chemistry, Catalysis, Ruthenium, Inorganic Chemistry, Organometallic Compounds, Organic chemistry, Physical and Theoretical Chemistry, Catalytic efficiency, Oxidation-Reduction |
| الوصف: | Mononuclear Ru-based water oxidation catalysts containing anionic ancillary ligands have shown promising catalytic efficiency and intriguing properties. However, their insolubility in water restricts a detailed mechanism investigation. In order to overcome this disadvantage, complexes [Ru(II)(bpc)(bpy)OH2](+) (1(+), bpc = 2,2'-bipyridine-6-carboxylate, bpy = 2,2'-bipyridine) and [Ru(II)(bpc)(pic)3](+) (2(+), pic = 4-picoline) were prepared and fully characterized, which features an anionic tridentate ligand and has enough solubility for spectroscopic study in water. Using Ce(IV) as an electron acceptor, both complexes are able to catalyze O2-evolving reaction with an impressive rate constant. On the basis of the electrochemical and kinetic studies, a water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS. Meanwhile, an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. The effect of anionic ligand regarding catalytic water oxidation was discussed explicitly in comparison with previously reported mononuclear Ru catalysts carrying neutral tridentate ligands, for example, 2,2':6',2″-terpyridine (tpy). When 2(+) was oxidized to the trivalent state, one of its picoline ligands dissociated from the Ru center. The rate constant of picoline dissociation was evaluated from time-resolved UV-vis spectra. |
| تدمد: | 1520-510X 0020-1669 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::4ef8aa00690b6e78043359f42eb56b37 https://doi.org/10.1021/ic302446h |
| رقم الأكسشن: | edsair.doi.dedup.....4ef8aa00690b6e78043359f42eb56b37 |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 1520510X 00201669 |
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