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Preparation and StructuralCharacterization of Ru II ‐DMSO and Ru III ‐DMSO‐substituted α‐Keggin‐type Phosphotungstates, [PW 11 O 39 Ru II DMSO] 5– and [PW 11 O 39 Ru III DMSO] 4– , and Catalytic Activity for Water Oxidation
Author(s) -
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
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100213
Subject(s) - chemistry , ruthenium , cyclic voltammetry , inorganic chemistry , nuclear chemistry , cerium , medicinal chemistry , catalysis , electrochemistry , organic chemistry , electrode
Ru II ‐ and Ru III ‐substituted α‐Keggin‐type phosphotungstates with a dimethyl sulfoxide (DMSO) ligand, [PW 11 O 39 Ru II DMSO] 5– ( 1 ) and [PW 11 O 39 Ru III DMSO] 4– ( 2 ), were synthesized. Compound 1 was prepared by reaction of [PW 11 O 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, 31 P NMR, 183 W NMR, 1 H NMR, and XANES (Ru K‐edge and L 3 ‐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.