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

doi:10.1002/zaac.201100213

Preparation and structural characterization of Ru^II-DMSO and Ru^III-DMSO-substituted α-Keggin-type phosphotungstates, [PW₁₁O₃₉Ru^IIDMSO]^5- and [PW ₁₁O₃₉Ru^IIIDMSO]^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 journal › Article › peer-review

28 Citations (Scopus)

Abstract

Ru^II-and Ru^III-substituted α-Keggin-type phosphotungstates with a dimethyl sulfoxide (DMSO) ligand, [PW ₁₁O₃₉Ru^IIDMSO]^5- (1) and [PW ₁₁O₃₉Ru^IIIDMSO]^4- (2), were synthesized. Compound 1 was prepared by reaction of [PW₁₁O ₃₉]^7- with [Ru^II(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 Ru^II is incorporated in the α-Keggin framework and coordinated by DMSO through a Ru-S bond. Cyclic voltammetry of 1 indicated that the incorporated Ru^II-DMSO is reversibly oxidizable to the Ru^III-DMSO derivative 2. Compound 1 showed catalytic activity for water oxidation in the presence of cerium ammonium nitrate as an oxidant.

Original language	English
Pages (from-to)	1467-1474
Number of pages	8
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	637
Issue number	11
DOIs	https://doi.org/10.1002/zaac.201100213
Publication status	Published - 2011 Sep
Externally published	Yes

Keywords

Oxidation
Polyoxometalates
Redox chemistry
Ruthenium
S ligands

ASJC Scopus subject areas

Inorganic Chemistry

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Sadakane, M., Rinn, N., Moroi, S., Kitatomi, H., Ozeki, T., Kurasawa, M., Itakura, M., Hayakawa, S., Kato, K., Miyamoto, M., Ogo, S., Ide, Y., & Sano, T. (2011). Preparation and structural characterization of Ru^II-DMSO and Ru^III-DMSO-substituted α-Keggin-type phosphotungstates, [PW₁₁O₃₉Ru^IIDMSO]^5- and [PW ₁₁O₃₉Ru^IIIDMSO]^4-, and catalytic activity for water oxidation. Zeitschrift fur Anorganische und Allgemeine Chemie, 637(11), 1467-1474. https://doi.org/10.1002/zaac.201100213

Preparation and structural characterization of Ru^II-DMSO and Ru^III-DMSO-substituted α-Keggin-type phosphotungstates, [PW₁₁O₃₉Ru^IIDMSO]^5- and [PW ₁₁O₃₉Ru^IIIDMSO]^4-, and catalytic activity for water oxidation. / Sadakane, Masahiro; Rinn, Niklas; Moroi, Sachie et al.

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

Research output: Contribution to journal › Article › peer-review

Sadakane, M, Rinn, N, Moroi, S, Kitatomi, H, Ozeki, T, Kurasawa, M, Itakura, M, Hayakawa, S, Kato, K, Miyamoto, M, Ogo, S, Ide, Y & Sano, T 2011, 'Preparation and structural characterization of Ru^II-DMSO and Ru^III-DMSO-substituted α-Keggin-type phosphotungstates, [PW₁₁O₃₉Ru^IIDMSO]^5- and [PW ₁₁O₃₉Ru^IIIDMSO]^4-, and catalytic activity for water oxidation', Zeitschrift fur Anorganische und Allgemeine Chemie, vol. 637, no. 11, pp. 1467-1474. https://doi.org/10.1002/zaac.201100213

Sadakane M, Rinn N, Moroi S, Kitatomi H, Ozeki T, Kurasawa M et al. Preparation and structural characterization of Ru^II-DMSO and Ru^III-DMSO-substituted α-Keggin-type phosphotungstates, [PW₁₁O₃₉Ru^IIDMSO]^5- and [PW ₁₁O₃₉Ru^IIIDMSO]^4-, and catalytic activity for water oxidation. Zeitschrift fur Anorganische und Allgemeine Chemie. 2011 Sep;637(11):1467-1474. https://doi.org/10.1002/zaac.201100213

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title = "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",

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.",

keywords = "Oxidation, Polyoxometalates, Redox chemistry, Ruthenium, S ligands",

author = "Masahiro Sadakane and Niklas Rinn and Sachie Moroi and Hiroaki Kitatomi and Tomoji Ozeki and Mariko Kurasawa and Masaya Itakura and Shinjiro Hayakawa and Kazuo Kato and Mayumi Miyamoto and Shuhei Ogo and Yusuke Ide and Tsuneji Sano",

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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

PY - 2011/9

Y1 - 2011/9

N2 - 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.

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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