Stabilization of Tetravalent Cerium upon Coordination of Unsaturated Heteropoly tungstate Anions

Nobuyuki Haraguchi, Yoshihiro Okaue, Toshiyuki Isobe, Yoshihisa Matsuda

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Monovacant Keggin derivative anions Xn+W11O39(12-n)- (X = P, Si, Ge, B) and a monovacant Dawson derivative anion P2W17O6110- were adopted as the ligand for cerium(III). The formation of the complexes [CeL](m-3)- and [CeL2](2m-3)- was confirmed by means of absorption spectroscopy, where Lm- denotes an unsaturated heteropolytungstate anion of P, Si, or Ge, while clear evidence for the complexation of BW11O399- was not obtained. Electrochemical behaviors of heteropolytungstocerates(III) were studied by cyclic and differential pulse voltammetry in aqueous solution. The redox potential of the cerium(IV/III) couple was considerably lowered (below +1 V vs Ag/AgCl) upon coordination of heteropolytungstate in aqueous solution at pH 4.5. The magnitude of the potential shift for [CeL](m-3)- increased in the order PW11O397-, P2W17O6110-, GeW11O398-, and SiW11O398-. A similar trend was observed for [CeL2](2m-3)- with larger potential shift than those of [CeL](m-3)-. The shift of the redox potential for cerium(IV/III) is caused primarily by the large negative charge of the unsaturated heteropolytungstate.

Original languageEnglish
Pages (from-to)1015-1020
Number of pages6
JournalInorganic chemistry
Issue number6
Publication statusPublished - Mar 1 1994

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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