Preparation and structural characterization of RuII-DMSO and RuIII-DMSO-substituted α-Keggin-type phosphotungstates, [PW11O39RuIIDMSO]5- and [PW 11O39RuIIIDMSO]4-, and catalytic activity for water oxidation

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)1467-1474
Number of pages8
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume637
Issue number11
DOIs
Publication statusPublished - 2011 Sep
Externally publishedYes

Keywords

  • Oxidation
  • Polyoxometalates
  • Redox chemistry
  • Ruthenium
  • S ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

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