Stabilization of high-valence ruthenium with silicotungstate ligands: Preparation, structural characterization, and redox studies of ruthenium(III)-substituted α-keggin-type silicotungstates with pyridine ligands, [SiW 11O 39Ru III(Py)] 5-

Masahiro Sadakane, Sachie Moroi, Yoshifumi Iimuro, Natalya Izarova, Ulrich Kortz, Shinjiro Hayakawa, Kazuo Kato, Shuhei Ogo, Yusuke Ide, Wataru Ueda, Tsuneji Sano

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Ruthenium(III)-substituted α-Keggin-type silicotungstates with pyridine-based ligands, [SiW 11O 39Ru III(Py)] 5-, (Py: pyridine (1), 4-pyridine-carboxylic acid (2), 4,4'-bipyridine (3), 4-pyridine-acetamide (4), and 4-pyridine-methanol (5)) were prepared by reacting [SiW 11O 39Ru III(H 2O)] 5- with the pyridine derivatives in water at 80°C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and 1H NMR spectroscopy, elemental analysis, titration, and X-ray absorption near-edge structure (XANES) analysis (Ru K-edge and L 3-edge). Single-crystal X-ray analysis of compounds 2, 3, and 4 revealed that Ru III was incorporated in the α-Keggin framework and was coordinated by pyridine derivatives through a Ru-N bond. In the solid state, compounds 2 and 3 formed a dimer through π-π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated Ru III-Py was reversibly oxidized into the Ru IV-Py derivative and reduced into the Ru II-Py derivative.

Original languageEnglish
Pages (from-to)1331-1339
Number of pages9
JournalChemistry - An Asian Journal
Volume7
Issue number6
DOIs
Publication statusPublished - 2012 Jun
Externally publishedYes

Fingerprint

Ruthenium
Oxidation-Reduction
Stabilization
Ligands
Derivatives
Cyclic voltammetry
X-Rays
Cesium
X ray analysis
X ray absorption
pyridine
Titration
Dimers
Nuclear magnetic resonance spectroscopy
Methanol
Magnetic Resonance Spectroscopy
Salts
Monomers
Single crystals
Water

Keywords

  • pi interactions
  • polyanions
  • redox chemistry
  • ruthenium
  • substituent effects

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Stabilization of high-valence ruthenium with silicotungstate ligands : Preparation, structural characterization, and redox studies of ruthenium(III)-substituted α-keggin-type silicotungstates with pyridine ligands, [SiW 11O 39Ru III(Py)] 5-. / Sadakane, Masahiro; Moroi, Sachie; Iimuro, Yoshifumi; Izarova, Natalya; Kortz, Ulrich; Hayakawa, Shinjiro; Kato, Kazuo; Ogo, Shuhei; Ide, Yusuke; Ueda, Wataru; Sano, Tsuneji.

In: Chemistry - An Asian Journal, Vol. 7, No. 6, 06.2012, p. 1331-1339.

Research output: Contribution to journalArticle

Sadakane, Masahiro ; Moroi, Sachie ; Iimuro, Yoshifumi ; Izarova, Natalya ; Kortz, Ulrich ; Hayakawa, Shinjiro ; Kato, Kazuo ; Ogo, Shuhei ; Ide, Yusuke ; Ueda, Wataru ; Sano, Tsuneji. / Stabilization of high-valence ruthenium with silicotungstate ligands : Preparation, structural characterization, and redox studies of ruthenium(III)-substituted α-keggin-type silicotungstates with pyridine ligands, [SiW 11O 39Ru III(Py)] 5-. In: Chemistry - An Asian Journal. 2012 ; Vol. 7, No. 6. pp. 1331-1339.
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abstract = "Ruthenium(III)-substituted α-Keggin-type silicotungstates with pyridine-based ligands, [SiW 11O 39Ru III(Py)] 5-, (Py: pyridine (1), 4-pyridine-carboxylic acid (2), 4,4'-bipyridine (3), 4-pyridine-acetamide (4), and 4-pyridine-methanol (5)) were prepared by reacting [SiW 11O 39Ru III(H 2O)] 5- with the pyridine derivatives in water at 80°C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and 1H NMR spectroscopy, elemental analysis, titration, and X-ray absorption near-edge structure (XANES) analysis (Ru K-edge and L 3-edge). Single-crystal X-ray analysis of compounds 2, 3, and 4 revealed that Ru III was incorporated in the α-Keggin framework and was coordinated by pyridine derivatives through a Ru-N bond. In the solid state, compounds 2 and 3 formed a dimer through π-π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated Ru III-Py was reversibly oxidized into the Ru IV-Py derivative and reduced into the Ru II-Py derivative.",
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T2 - Preparation, structural characterization, and redox studies of ruthenium(III)-substituted α-keggin-type silicotungstates with pyridine ligands, [SiW 11O 39Ru III(Py)] 5-

AU - Sadakane, Masahiro

AU - Moroi, Sachie

AU - Iimuro, Yoshifumi

AU - Izarova, Natalya

AU - Kortz, Ulrich

AU - Hayakawa, Shinjiro

AU - Kato, Kazuo

AU - Ogo, Shuhei

AU - Ide, Yusuke

AU - Ueda, Wataru

AU - Sano, Tsuneji

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AB - Ruthenium(III)-substituted α-Keggin-type silicotungstates with pyridine-based ligands, [SiW 11O 39Ru III(Py)] 5-, (Py: pyridine (1), 4-pyridine-carboxylic acid (2), 4,4'-bipyridine (3), 4-pyridine-acetamide (4), and 4-pyridine-methanol (5)) were prepared by reacting [SiW 11O 39Ru III(H 2O)] 5- with the pyridine derivatives in water at 80°C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and 1H NMR spectroscopy, elemental analysis, titration, and X-ray absorption near-edge structure (XANES) analysis (Ru K-edge and L 3-edge). Single-crystal X-ray analysis of compounds 2, 3, and 4 revealed that Ru III was incorporated in the α-Keggin framework and was coordinated by pyridine derivatives through a Ru-N bond. In the solid state, compounds 2 and 3 formed a dimer through π-π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated Ru III-Py was reversibly oxidized into the Ru IV-Py derivative and reduced into the Ru II-Py derivative.

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KW - substituent effects

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