TY - JOUR
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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U2 - 10.1002/zaac.201100213
DO - 10.1002/zaac.201100213
M3 - Article
AN - SCOPUS:80053188804
VL - 637
SP - 1467
EP - 1474
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
SN - 0044-2313
IS - 11
ER -