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 language | English |
|---|---|
| Pages (from-to) | 1015-1020 |
| Number of pages | 6 |
| Journal | Inorganic chemistry |
| Volume | 33 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Mar 1 1994 |
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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 journal › Article
}
TY - JOUR
T1 - Stabilization of Tetravalent Cerium upon Coordination of Unsaturated Heteropoly tungstate Anions
AU - Haraguchi, Nobuyuki
AU - Okaue, Yoshihiro
AU - Isobe, Toshiyuki
AU - Matsuda, Yoshihisa
PY - 1994/3/1
Y1 - 1994/3/1
N2 - 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.
AB - 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.
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U2 - 10.1021/ic00084a008
DO - 10.1021/ic00084a008
M3 - Article
AN - SCOPUS:0000649180
VL - 33
SP - 1015
EP - 1020
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 6
ER -