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

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Abstract

The carbonyl-ruthenium substituted undecatungstosilicate [α-SiW 11O39RuII(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 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 situ IR coupled with electrolysis. The oxidized ruthenium(iii) derivative slowly released CO in aqueous solution, resulting in the aqua species [α-SiW 11O39RuIII(H2O)]5- and then the dimeric POM species by condensation. Furthermore, 1 could be converted to the corresponding aqua polyanion by photo-irradiation.

Original languageEnglish
Pages (from-to)6692-6698
Number of pages7
JournalDalton Transactions
Issue number47
DOIs
Publication statusPublished - 2008 Dec 2
Externally publishedYes

ASJC Scopus subject areas

  • Inorganic Chemistry

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    Sadakane, M., Iimuro, Y., Tsukuma, D., Bassil, B. S., Dickman, M. H., Kortz, U., Zhang, Y., Ye, S., & Ueda, W. (2008). Carbonyl-ruthenium substituted α-Keggin-tungstosilicate, [α-SiW11O39RuII(CO)]6-: Synthesis, structure, redox studies and reactivity. Dalton Transactions, (47), 6692-6698. https://doi.org/10.1039/b810987g