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

Research output: Contribution to journalArticle

25 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

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Dimethyl Sulfoxide
Catalyst activity
Oxidation
Water
Cesium
Nuclear magnetic resonance
Cyclic voltammetry
Salts
Cerium
Bromine
Oxidants
Structural analysis
Single crystals
Ligands
Derivatives
Chemical analysis

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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. / Sadakane, Masahiro; Rinn, Niklas; Moroi, Sachie; Kitatomi, Hiroaki; Ozeki, Tomoji; Kurasawa, Mariko; Itakura, Masaya; Hayakawa, Shinjiro; Kato, Kazuo; Miyamoto, Mayumi; Ogo, Shuhei; Ide, Yusuke; Sano, Tsuneji.

In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 637, No. 11, 09.2011, p. 1467-1474.

Research output: Contribution to journalArticle

Sadakane, Masahiro ; Rinn, Niklas ; Moroi, Sachie ; Kitatomi, Hiroaki ; Ozeki, Tomoji ; Kurasawa, Mariko ; Itakura, Masaya ; Hayakawa, Shinjiro ; Kato, Kazuo ; Miyamoto, Mayumi ; Ogo, Shuhei ; Ide, Yusuke ; Sano, Tsuneji. / 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. In: Zeitschrift fur Anorganische und Allgemeine Chemie. 2011 ; Vol. 637, No. 11. pp. 1467-1474.
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T1 - 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

AU - Sadakane, Masahiro

AU - Rinn, Niklas

AU - Moroi, Sachie

AU - Kitatomi, Hiroaki

AU - Ozeki, Tomoji

AU - Kurasawa, Mariko

AU - Itakura, Masaya

AU - Hayakawa, Shinjiro

AU - Kato, Kazuo

AU - Miyamoto, Mayumi

AU - Ogo, Shuhei

AU - Ide, Yusuke

AU - Sano, Tsuneji

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AB - 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.

KW - Oxidation

KW - Polyoxometalates

KW - Redox chemistry

KW - Ruthenium

KW - S ligands

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