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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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Supplementary files

Article information


Submitted
30 Jun 2008
Accepted
02 Sep 2008
First published
20 Oct 2008

Dalton Trans., 2008, 6692-6698
Article type
Paper

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, 6692 DOI: 10.1039/B810987G

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