Preparation and Redox Studies of 伪1- and 伪2-Isomers of Mono-Ru-Substituted Dawson-type Phosphotungstates with a DMSO Ligand: [伪1/伪2-P2W17
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- 作者：Shuhei Ogo ; Noriko Shimizu ; Kensuke Nishiki ; Nobuhiro Yasuda ; Tsutomu Mizuta ; Tsuneji Sano ; Masahiro Sadakane
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：April 7, 2014
- 年：2014
- 卷：53
- 期：7
- 页码：3526-3539
- 全文大小：701K
- 年卷期：v.53,no.7(April 7, 2014)
- ISSN：1520-510X
文摘
Both 伪1- and 伪2-isomers of mono-Ru-substituted Dawson-type heteropolytungstates with a DMSO ligand, [伪1-P2W17O61RuII(DMSO)]8鈥?/sup> and [伪2-P2W17O61RuII(DMSO)]8鈥?/sup>, are prepared from the 伪2-isomer of a monolacunary derivative, [伪2-P2W17O61]10鈥?/sup>. Reaction of [伪2-P2W17O61]10鈥?/sup> with Ru(DMSO)4Cl2 under hydrothermal conditions produces [伪2-P2W17O61RuII(DMSO)]8鈥?/sup> as a main product together with [伪1-P2W17O61RuII(DMSO)]8鈥?/sup>, [PW11O39RuII(DMSO)]5鈥?/sup>, and [P2W18O62]6鈥?/sup> as byproducts. By addition of KCl to the reaction mixture, K8[伪2-P2W17O61RuII(DMSO)] is isolated in a moderate yield. On the other hand, reaction of [伪2-P2W17O61]10鈥?/sup> with Ru2(benzene)2Cl4 under hydrothermal conditions produces an isomeric mixture of [P2W17O61RuIII(H2O)]7鈥?/sup> (伪1-isomer/伪2-isomer ratio: ca. 8/1) as a main product together with [PW11O39RuIII(H2O)]4鈥?/sup> and [P2W18O62]6鈥?/sup> as byproducts. By addition of acetone to the reaction mixture, K7[P2W17O61RuIII(H2O)] is isolated in a good yield. Reaction of [P2W17O61RuIII(H2O)]7鈥?/sup> with DMSO produces [伪1-P2W17O61RuIII(DMSO)]7鈥?/sup> as a main product and [伪2-P2W17O61RuIII(DMSO)]7鈥?/sup> as a minor product. By addition of KCl and acetone, the 伪1-isomer K8[伪1-P2W17O61RuII(DMSO)] is isolated in a good yield. Both compounds are fully analyzed by CV, NMR (1H, 13C, 31P, and 183W), IR, UV鈥搗is, elemental analysis, mass spectroscopy, and single-crystal structure analysis. Assuming that isomerization does not occur during the reaction of [P2W17O61RuIII(H2O)]7鈥?/sup> with DMSO, the isolated [P2W17O61RuIII(H2O)]7鈥?/sup> contains the 伪1-isomer as a main compound with the 伪2-isomer as a minor compound. Unusual transformation of the 伪2-isomer of [P2W17O61]10鈥?/sup> to the 伪1-isomer occurs. Redox behaviors of [伪1-P2W17O61RuII(DMSO)]8鈥?/sup> and [伪2-P2W17O61RuII(DMSO)]8鈥?/sup> are compared together with Ru(DMSO)-substituted 伪-Keggin-type heteropolytungstates, [伪-XW11O39Ru(DMSO)]n鈭?/sup> (X = Si, Ge, and P).