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Issue 47, 2008
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Carbonyl–ruthenium substituted α-Keggin-tungstosilicate, [α-SiW11O39RuII(CO)]6−: synthesis, structure, redox studies and reactivity

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Abstract

The carbonyl–ruthenium substituted undecatungstosilicate [α-SiW11O39RuII(CO)]6− (1) was isolated as a caesium salt and successfully characterized by using 183W and 13C NMR, elemental analysis, IR, UV-vis and cyclic voltammetry (CV). Polyanion 1 represents the first example of a metal–carbonyl moiety being fully incorporated into the polyoxometalate (POM). As a result, the Ru(CO) moiety became redox active and was reversibly oxidized to the one-electron ruthenium(III) derivative, [α-SiW11O39RuIII(CO)]5−. This RuIII(CO) moiety was unexpectedly stable in aqueous solution compared to the organo–ruthenium carbonyl derivatives and could be detected by using UV-vis and in situIR coupled with electrolysis. The oxidized ruthenium(III) derivative slowly released CO in aqueous solution, resulting in the aqua species [α-SiW11O39RuIII(H2O)]5− and then the dimeric POM species by condensation. Furthermore, 1 could be converted to the corresponding aqua polyanion by photo-irradiation.

Graphical abstract: Carbonyl–ruthenium substituted α-Keggin-tungstosilicate, [α-SiW11O39RuII(CO)]6−: synthesis, structure, redox studies and reactivity

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Publication details

The article was received on 30 Jun 2008, accepted on 02 Sep 2008 and first published on 20 Oct 2008


Article type: Paper
DOI: 10.1039/B810987G
Citation: Dalton Trans., 2008,0, 6692-6698
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    Carbonyl–ruthenium substituted α-Keggin-tungstosilicate, [α-SiW11O39RuII(CO)]6−: synthesis, structure, redox studies and reactivity

    M. Sadakane, Y. Iimuro, D. Tsukuma, B. S. Bassil, M. H. Dickman, U. Kortz, Y. Zhang, S. Ye and W. Ueda, Dalton Trans., 2008, 0, 6692
    DOI: 10.1039/B810987G

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