Stabilization of Tetravalent Cerium upon Coordination of Unsaturated Heteropoly tungstate Anions

Nobuyuki Haraguchi, Yoshihiro Okaue, Toshiyuki Isobe, Yoshihisa Matsuda

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Abstract

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
Volume33
Issue number6
DOIs
Publication statusPublished - Mar 1 1994

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Cerium
tungstates
cerium
Anions
Stabilization
stabilization
anions
Polysilicon
Derivatives
shift
Voltammetry
aqueous solutions
Complexation
Absorption spectroscopy
Ligands
absorption spectroscopy
trends
ligands
tungstate
pulses

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Stabilization of Tetravalent Cerium upon Coordination of Unsaturated Heteropoly tungstate Anions. / Haraguchi, Nobuyuki; Okaue, Yoshihiro; Isobe, Toshiyuki; Matsuda, Yoshihisa.

In: Inorganic chemistry, Vol. 33, No. 6, 01.03.1994, p. 1015-1020.

Research output: Contribution to journalArticle

Haraguchi, Nobuyuki ; Okaue, Yoshihiro ; Isobe, Toshiyuki ; Matsuda, Yoshihisa. / Stabilization of Tetravalent Cerium upon Coordination of Unsaturated Heteropoly tungstate Anions. In: Inorganic chemistry. 1994 ; Vol. 33, No. 6. pp. 1015-1020.
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