Preparation and StructuralCharacterization of RuII‐DMSO and RuIII‐DMSO‐substituted α‐Keggin‐type Phosphotungstates, [PW11O39RuIIDMSO]5– and [PW11O39RuIIIDMSO]4–, and Catalytic Activity for Water Oxidation |
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| Authors: | Prof Dr Masahiro Sadakane Niklas Rinn Sachie Moroi Hiroaki Kitatomi Tomoji Ozeki Mariko Kurasawa Masaya Itakura Shinjiro Hayakawa Kazuo Kato Mayumi Miyamoto Shuhei Ogo Yusuke Ide Tsuneji Sano |
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| Institution: | 1. Chemistry and Chemical Engineering, Graduate School of Engineering Hiroshima University 1‐4‐1 Kagamiyama Higashi‐Hiroshima, 739–8527, Japan;2. PRESTO, Japan Science and Technology Agency (JST) 4‐1‐8 Honcho Kawaguchi, Saitama, 332–0012, Japan;3. Department of Chemistry and Materials Science Tokyo Institute of Technology 2‐12‐1, O‐okayama Meguro‐ku, Tokyo, 152–8551, Japan;4. Research and Utilization Division Japan Synchrotron Radiation Research Institute (JASRI) SPring‐8, 1–1‐1 Kouto Sayo, Hyogo, 679–5198, Japan |
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| Abstract: | RuII‐ and RuIII‐substituted α‐Keggin‐type phosphotungstates with a dimethyl sulfoxide (DMSO) ligand, PW11O39RuIIDMSO]5– ( 1 ) and PW11O39RuIIIDMSO]4– ( 2 ), were synthesized. Compound 1 was prepared by reaction of PW11O39]7– with RuII(DMSO)4]Cl2 in water at 125 °C under hydrothermal conditions and was isolated as a cesium salt. Compound 2 was prepared by reaction of 1 with bromine in water at 60 °C and was isolated as a cesium salt. The compounds were characterized by cyclic voltammetry, elemental analysis, UV/Vis, IR,31P NMR, 183W NMR, 1H NMR, and XANES (Ru K‐edge and L3‐edge)spectroscopic methods. Single crystal structural analysis of 1 revealed that RuII is incorporated in the α‐Keggin framework and coordinated by DMSO through a Ru–S bond. Cyclic voltammetry of 1 indicated that the incorporated RuII‐DMSO is reversibly oxidizable to the RuIII‐DMSO derivative 2 . Compound 1 showed catalytic activity for water oxidation in the presence of cerium ammonium nitrate as an oxidant. |
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| Keywords: | Polyoxometalates Ruthenium S ligands Redox chemistry Oxidation |
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