Determination of α-Keggin structure of [GeW11O39RuIII(H2O)]5−. Reaction of [GeW11O39RuIII(H2O)]5−with dimethyl sulfoxide to form [GeW11O39RuIII(dmso)]5−and their structural characterization

Shuhei Ogo, Noriko Shimizu, Tomoji Ozeki, Yusuke Kobayashi, Yusuke Ide, Tsuneji Sano, Masahiro Sadakane

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Abstract

Reaction of ruthenium(III)-substituted Keggin-type germanotungstate [GeW11O39RuIII(H2O)]5−(1) with a dimethyl sulfoxide (dmso) produced a dmso-coordinating derivative [GeW11O39RuIII(dmso)]5−(2). Structural characterization of compound 2 by using cyclic voltammetry, UV-Vis spectroscopy, IR spectroscopy, elemental analysis, 1H-NMR spectroscopy and single crystal structure analysis (monoclinic, P21/c, a = 13.461(1), b = 20.198(1), c = 18.078(1), β = 90.426(1), Z = 4) revealed that RuIIIwas incorporated in the α-Keggin-type framework and coordinated by dmso through an Ru–S bond. The IR spectra of 1 and 2 were very similar, indicating that 1 also has an α-Keggin structure. Cyclic voltammetry indicated that the incorporated RuIII-dmso was reversibly reduced to the RuII-dmso derivative and oxidized to the RuIV-dmso derivative. The redox potential in [α-XW11O39RuIII/II(dmso)]n−(X = P, Ge, Si) decreased in the order of P > Ge > Si. Reaction of the complex 2 with ascorbic acid produced a one-electron-reduced compound [α-GeW11O39RuII(dmso)]6−.

Original languageEnglish
Pages (from-to)2540-2545
Number of pages6
JournalJournal of the Chemical Society. Dalton Transactions
Volume42
Issue number2
DOIs
Publication statusPublished - 2013 Jan 22
Externally publishedYes

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Dimethyl Sulfoxide
Derivatives
Cyclic voltammetry
Ruthenium
Ultraviolet spectroscopy
Nuclear magnetic resonance spectroscopy
Ascorbic Acid
Infrared spectroscopy
Crystal structure
Single crystals
Electrons
Chemical analysis

ASJC Scopus subject areas

  • Chemistry(all)

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Determination of α-Keggin structure of [GeW11O39RuIII(H2O)]5−. Reaction of [GeW11O39RuIII(H2O)]5−with dimethyl sulfoxide to form [GeW11O39RuIII(dmso)]5−and their structural characterization. / Ogo, Shuhei; Shimizu, Noriko; Ozeki, Tomoji; Kobayashi, Yusuke; Ide, Yusuke; Sano, Tsuneji; Sadakane, Masahiro.

In: Journal of the Chemical Society. Dalton Transactions, Vol. 42, No. 2, 22.01.2013, p. 2540-2545.

Research output: Contribution to journalArticle

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abstract = "Reaction of ruthenium(III)-substituted Keggin-type germanotungstate [GeW11O39RuIII(H2O)]5−(1) with a dimethyl sulfoxide (dmso) produced a dmso-coordinating derivative [GeW11O39RuIII(dmso)]5−(2). Structural characterization of compound 2 by using cyclic voltammetry, UV-Vis spectroscopy, IR spectroscopy, elemental analysis, 1H-NMR spectroscopy and single crystal structure analysis (monoclinic, P21/c, a = 13.461(1), b = 20.198(1), c = 18.078(1), β = 90.426(1), Z = 4) revealed that RuIIIwas incorporated in the α-Keggin-type framework and coordinated by dmso through an Ru–S bond. The IR spectra of 1 and 2 were very similar, indicating that 1 also has an α-Keggin structure. Cyclic voltammetry indicated that the incorporated RuIII-dmso was reversibly reduced to the RuII-dmso derivative and oxidized to the RuIV-dmso derivative. The redox potential in [α-XW11O39RuIII/II(dmso)]n−(X = P, Ge, Si) decreased in the order of P > Ge > Si. Reaction of the complex 2 with ascorbic acid produced a one-electron-reduced compound [α-GeW11O39RuII(dmso)]6−.",
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AU - Ozeki, Tomoji

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AU - Sano, Tsuneji

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