RuII-and RuIII-substituted α-Keggin-type phosphotungstates with a dimethyl sulfoxide (DMSO) ligand, [PW 11O39RuIIDMSO]5- (1) and [PW 11O39RuIIIDMSO]4- (2), were synthesized. Compound 1 was prepared by reaction of [PW11O 39]7- with [RuII(DMSO)4]Cl 2 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.
|Number of pages||8|
|Journal||Zeitschrift fur Anorganische und Allgemeine Chemie|
|Publication status||Published - 2011 Sep|
- Redox chemistry
- S ligands
ASJC Scopus subject areas
- Inorganic Chemistry