Preparation and redox studies of α1- and α2-isomers of mono-Ru-substituted dawson-type phosphotungstates with a DMSO Ligand: [α12-P 2W17O61RuII(DMSO)]8-

Shuhei Ogo, Noriko Shimizu, Kensuke Nishiki, Nobuhiro Yasuda, Tsutomu Mizuta, Tsuneji Sano, Masahiro Sadakane

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Both α1- and α2-isomers of mono-Ru-substituted Dawson-type heteropolytungstates with a DMSO ligand, [α1-P2W17O61Ru II(DMSO)]8- and [α2-P2W 17O61RuII(DMSO)]8-, are prepared from the α2-isomer of a monolacunary derivative, [α2-P2W17O61]10-. Reaction of [α2-P2W17O61] 10- with Ru(DMSO)4Cl2 under hydrothermal conditions produces [α2-P2W17O 61RuII(DMSO)]8- as a main product together with [α1-P2W17O61Ru II(DMSO)]8-, [PW11O39Ru II(DMSO)]5-, and [P2W18O 62]6- as byproducts. By addition of KCl to the reaction mixture, K82-P2W17O 61RuII(DMSO)] is isolated in a moderate yield. On the other hand, reaction of [α2-P2W17O 61]10- with Ru2(benzene)2Cl 4 under hydrothermal conditions produces an isomeric mixture of [P2W17O61RuIII(H2O)] 7-1-isomer/α2-isomer ratio: ca. 8/1) as a main product together with [PW11O39Ru III(H2O)]4- and [P2W 18O62]6- as byproducts. By addition of acetone to the reaction mixture, K7[P2W17O 61RuIII(H2O)] is isolated in a good yield. Reaction of [P2W17O61RuIII(H 2O)]7- with DMSO produces [α1-P 2W17O61RuIII(DMSO)]7- as a main product and [α2-P2W17O 61RuIII(DMSO)]7- as a minor product. By addition of KCl and acetone, the α1-isomer K 81-P2W17O 61RuII(DMSO)] is isolated in a good yield. Both compounds are fully analyzed by CV, NMR (1H, 13C, 31P, and 183W), IR, UV-vis, elemental analysis, mass spectroscopy, and single-crystal structure analysis. Assuming that isomerization does not occur during the reaction of [P2W17O61Ru III(H2O)]7- with DMSO, the isolated [P 2W17O61RuIII(H2O)] 7- contains the α1-isomer as a main compound with the α2-isomer as a minor compound. Unusual transformation of the α2-isomer of [P2W17O 61]10- to the α1-isomer occurs. Redox behaviors of [α1-P2W17O 61RuII(DMSO)]8- and [α2-P 2W17O61RuII(DMSO)]8- are compared together with Ru(DMSO)-substituted α-Keggin-type heteropolytungstates, [α-XW11O39Ru(DMSO)] n- (X = Si, Ge, and P).

Original languageEnglish
Pages (from-to)3526-3539
Number of pages14
JournalInorganic Chemistry
Issue number7
Publication statusPublished - 2014 Apr 7
Externally publishedYes


ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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