Determination of α-Keggin structure of [GeW11O39Ru(III)(H2O)]5-. Reaction of [GeW11O39Ru(III)(H2O)]5- with dimethyl sulfoxide to form [GeW11O39Ru(III)(dmso)]5- and their structural characterization

Shuhei Ogo; Noriko Shimizu; Tomoji Ozeki; Yusuke Kobayashi; Yusuke Ide; Tsuneji Sano; Masahiro Sadakane

doi:10.1039/c2dt32038j

Determination of α-Keggin structure of [GeW11O39Ru(III)(H2O)]5-. Reaction of [GeW11O39Ru(III)(H2O)]5- with dimethyl sulfoxide to form [GeW11O39Ru(III)(dmso)]5- and their structural characterization

Dalton Trans. 2013 Feb 21;42(7):2540-5. doi: 10.1039/c2dt32038j. Epub 2012 Dec 7.

Authors

Shuhei Ogo¹, Noriko Shimizu, Tomoji Ozeki, Yusuke Kobayashi, Yusuke Ide, Tsuneji Sano, Masahiro Sadakane

Affiliation

¹ Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, 739-8527, Japan.

PMID: 23223676
DOI: 10.1039/c2dt32038j

Abstract

Reaction of ruthenium((III))-substituted Keggin-type germanotungstate [GeW(11)O(39)Ru(III)(H(2)O)](5-) (1) with a dimethyl sulfoxide (dmso) produced a dmso-coordinating derivative [GeW(11)O(39)Ru(III)(dmso)](5-) (2). Structural characterization of compound 2 by using cyclic voltammetry, UV-Vis spectroscopy, IR spectroscopy, elemental analysis, (1)H-NMR spectroscopy and single crystal structure analysis (monoclinic, P2(1)/c, a = 13.461(1), b = 20.198(1), c = 18.078(1), β = 90.426(1), Z = 4) revealed that Ru(III) was incorporated in the α-Keggin-type framework and coordinated by dmso through an Ru-S bond. The IR spectra of 1 and 2 were very similar, indicating that 1 also has an α-Keggin structure. Cyclic voltammetry indicated that the incorporated Ru(III)-dmso was reversibly reduced to the Ru(II)-dmso derivative and oxidized to the Ru(IV)-dmso derivative. The redox potential in [α-XW(11)O(39)Ru(III/II)(dmso)](n-) (X = P, Ge, Si) decreased in the order of P > Ge > Si. Reaction of the complex 2 with ascorbic acid produced a one-electron-reduced compound [α-GeW(11)O(39)Ru(II)(dmso)](6-).