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Issue 26, 2007
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Dimerization of mono-ruthenium substituted α-Keggin-type tungstosilicate [α-SiW11O39RuIII(H2O)]5− to µ-oxo-bridged dimer in aqueous solution: synthesis, structure, and redox studies

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Abstract

We report the dimerization of a mono-ruthenium(III) substituted α-Keggin-type tungstosilicate [α-SiW11O39RuIII(H2O)]5− to a µ-oxo-bridged dimer [{α-SiW11O39Rum}2O]n (m = III, n = 12; m = IV/III, n = 11; m = IV, n = 10). Single crystal X-ray structure analysis of Rb10[{α-SiW11O39RuIV}2O]·9.5H2O (triclinic, P[1 with combining macron], with a = 12.7650(6) Å, b = 18.9399(10) Å, c = 20.2290(10) Å, α = 72.876(3)°, β = 88.447(3)°, γ = 80.926(3)°, V = 4614.5(4) Å3, Z = 2) reveals that two mono-ruthenium substituted tungstosilicate α-Keggin units are connected through µ-oxo-bridging Ru–O–Ru bonds. Solution 183W-NMR of [{SiW11O39RuIV}2O]10− resulted in six peaks (−63, −92, −110, −128, −132, and −143 ppm, intensities 2 : 2 : 1 : 2 : 2 : 2) confirming that the µ-oxo bridged dimer structure is maintained in aqueous solution. The dimerization mechanism is presumably initiated by deprotonation of the aqua-ruthenium complex [α-SiW11O39RuIII(H2O)]5− leading to a hydroxy-ruthenium complex [α-SiW11O39RuIII(OH)]6−. Dimerization of two hydroxy-ruthenium complexes produces the µ-oxo bridged dimer [{α-SiW11O39RuIII}2O]12− and a water molecule. The Ru(III) containing dimer is oxidized by molecular oxygen to produce a mixed valence species [{α-SiW11O39RuIV-III}2O]11−, and further oxidation results in the Ru(IV) containing [{α-SiW11O39RuIV}2O]10−.

Graphical abstract: Dimerization of mono-ruthenium substituted α-Keggin-type tungstosilicate [α-SiW11O39RuIII(H2O)]5− to µ-oxo-bridged dimer in aqueous solution: synthesis, structure, and redox studies

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Publication details

The article was received on 23 Feb 2007, accepted on 16 Apr 2007 and first published on 10 May 2007


Article type: Paper
DOI: 10.1039/B702813J
Citation: Dalton Trans., 2007,0, 2833-2838
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    Dimerization of mono-ruthenium substituted α-Keggin-type tungstosilicate [α-SiW11O39RuIII(H2O)]5− to µ-oxo-bridged dimer in aqueous solution: synthesis, structure, and redox studies

    M. Sadakane, D. Tsukuma, M. H. Dickman, B. S. Bassil, U. Kortz, M. Capron and W. Ueda, Dalton Trans., 2007, 0, 2833
    DOI: 10.1039/B702813J

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