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

Masahiro Sadakane; Yoshifumi Iimuro; Daisuke Tsukuma; Bassem S. Bassil; Michael H. Dickman; Ulrich Kortz; Yi Zhang; Shen Ye; Wataru Ueda

doi:10.1039/B810987G

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Carbonyl–ruthenium substituted α-Keggin-tungstosilicate, [α-SiW₁₁O₃₉Ru^II(CO)]⁶⁻: synthesis, structure, redox studies and reactivity†

Masahiro Sadakane,*^a Yoshifumi Iimuro,^a Daisuke Tsukuma,^a Bassem S. Bassil,^b Michael H. Dickman,^b Ulrich Kortz,^b Yi Zhang,^a Shen Ye^ac and Wataru Ueda^a

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* Corresponding authors

^a Catalysis Research Center, Hokkaido University, N-21, W-10, Sapporo, Japan
E-mail: sadakane@cat.hokudai.ac.jp
Fax: +81 11 706 9163
Tel: +81 11 706 9166

^b School of Engineering and Science, Jacobs University, P. O. Box 750561, 28725 Bremen, Germany

^c PRESTO, Japan Science and Technology Agency (JST), Japan

Abstract

The carbonyl–ruthenium substituted undecatungstosilicate [α-SiW₁₁O₃₉Ru^II(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-SiW₁₁O₃₉Ru^III(CO)]⁵⁻. This Ru^III(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-SiW₁₁O₃₉Ru^III(H₂O)]⁵⁻ and then the dimeric POM species by condensation. Furthermore, 1 could be converted to the corresponding aqua polyanion by photo-irradiation.

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Supplementary files

UV-vis and CV of the electrochemically generated [SiW₁₁O₃₉Ru^III(CO)]⁵⁻ in phosphate solution (pH 1.8 and pH 4.5) (Fig.S1). IR spectrum of the isolated solid by adding CsCl to a solutioncontaining [SiW₁₁O₃₉Ru^III(CO)]⁵⁻ (Fig. S2) PDF (251K)

Article information

DOI: https://doi.org/10.1039/B810987G
Article type: Paper
Submitted: 30 Jun 2008
Accepted: 02 Sep 2008
First published: 20 Oct 2008

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Dalton Trans., 2008, 6692-6698

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Carbonyl–ruthenium substituted α-Keggin-tungstosilicate, [α-SiW₁₁O₃₉Ru^II(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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Dalton Transactions