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Issue 32, 2009
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Synthesis and crystal structure of pseudo-sandwich-type heteropolytungstates functionalized by organometallic ruthenium(II)

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Abstract

The reaction between [XW9O34]9− (X = As, P) and [RuC6H6Cl2]2 in aqueous buffer solution (pH 6.0) leads to the isolation of two pseudo-sandwich-type heteropolytungstates KNa6[(RuC6H6)AsW9O34]·17H2O (As-1) and Na7[(RuC6H6)PW9O34]·14H2O (P-2). Single-crystal X-ray diffraction analyses reveal that the two compounds have the following features: (1) in two polyanions [(RuC6H6)XW9O34]7− (X = As, 1; P, 2), the (RuC6H6) unit is linked via three Ru–O(W) bridges to the side of the trilacunary polyanion, while the lacunary site is still free; (2) the units 1 and 2 are connected exclusively by a central Na cation cluster to form the pseudo-sandwich-type heteropolytungstates; and (3) the pseudo-sandwich-type heteropolytungstates are further connected by Na or K cations to construct the 2D and 3D structures. Furthermore, the electrochemical behaviours of As-1 and P-2 in aqueous solution (1.0 M LiCl + HCl, pH 3.0) have been investigated. Two compounds exhibit the expected reduction processes of the W atoms in a negative potential range and the oxidation of the Ru center in a positive potential range. The results of the electrocatalytic experiments reveal that the compound P-2 has electrocatalytic activity towards the reduction of nitrate.

Graphical abstract: Synthesis and crystal structure of pseudo-sandwich-type heteropolytungstates functionalized by organometallic ruthenium(ii)

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Publication details

The article was received on 03 Dec 2008, accepted on 14 May 2009 and first published on 01 Jul 2009


Article type: Paper
DOI: 10.1039/B821750E
Citation: Dalton Trans., 2009,0, 6345-6353
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    Synthesis and crystal structure of pseudo-sandwich-type heteropolytungstates functionalized by organometallic ruthenium(II)

    L. Bi, G. Hou, B. Li, L. Wu and U. Kortz, Dalton Trans., 2009, 0, 6345
    DOI: 10.1039/B821750E

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