Synthesis and characterization of copper-, zinc-, manganese-, and cobalt-substituted dimeric heteropolyanions, [(α-XW9O33)2M3(H2O)3]n- (n=12, X = AsIII, SbIII, m = Cu2+, Zn2+; n=10, X = SeIV, TeIV, M = Cu2+) and [(α-AsW9O33)2WO(H2O)M2(H2O)2]10- (M = Zn2+, Mn2+, Co2+)

被引:257
作者
Kortz, U
Al-Kassem, NK
Savelieff, MG
Al Kadi, NA
Sadakane, M
机构
[1] Amer Univ Beirut, Dept Chem, Beirut, Lebanon
[2] Georgetown Univ, Dept Chem, Washington, DC 20057 USA
关键词
D O I
10.1021/ic0101477
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Interaction of the lacunary [alpha -XW9O33](9-) (X = As-III, Sb-III) with Cu2+ and Zn2+ ions in neutral, aqueous medium leads to the formation of dimeric polyoxoanions, [(alpha -XW9O33)(2)M-3(H2O)(3)](12-) (M = Cu2+, Zn2+; X = As-III, Sb-III), in high yield. The selenium and tellurium analogues of the copper-containing heteropolyanions are also reported: [(alpha -XW9O33)(2)Cu-3(H2O)(3)](10-) (X = Se-IV, Te-IV). The polyanions consist of two [alpha -XW9O33] units joined by three equivalent Cu2+ (X = As, Sb, Se, Te) or Zn2+ (X = As, Sb) ions. All copper and zinc ions have one terminal water molecule resulting in square-pyramidal coordination geometry. Therefore, the title anions have idealized DY, symmetry. The space between the three transition metal ions is occupied by three sodium ions (M = Cu2+, Zn2+: X = As-III, Sb-III) or potassium ions (M = Cu2+; X = Se-IV, Te-IV) leading to a central belt of six metal atoms alternating in position. Reaction of [alpha -AsW9O33](9-) with Zn2+, Co2+, and Mn2+ ions in acidic medium (pH = 4-5) results in the same structural type but with a lower degree of transition-metal substitution, [(alpha -AsW9O33)(2)-WO(H2O)M-2(H2O)(2)](10-) (M = Zn2+, Co2+, Mn2+). All nine compounds are characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. The solution properties of [(alpha -XW9O33)(2)Zn-3(H2O)(3)](12-) (X = As-III Sb-III) were also studied by W-183-NMR spectroscopy.
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页码:4742 / 4749
页数:8
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