Confirmation of the Semivacant Wells-Dawson Polyoxotungstate Skeleton. The Structures of [Ce{X(H4)W17O61}2]19- (X = P, As) Indicate the Probable

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• 作者：Nebebech Belai ; Michael H. Dickman ; Michael T. Pope ; Roland Contant ; Bineta Keita ; Israel-Martyr Mbomekalle ; and Louis Nadjo
• 刊名：Inorganic Chemistry
• 出版年：2005
• 出版时间：January 24, 2005
• 年：2005
• 卷：44
• 期：2
• 页码：169 - 171
• 全文大小：114K
• 年卷期：v.44,no.2(January 24, 2005)
• ISSN：1520-510X

文摘

Reaction of Ce(III) with lacunary versions of [H₄XW₁₈O₆₂]^7- (X =P, As) yields the 1:2 complexes [Ce(H₄XW₁₇O₆₁]^19- (X = As, 1;P, 2) in good yield, characterized in solution and the solid stateby NMR spectroscopy and X-ray crystallographic analysis, respectively. The structures confirm a syn C₂ conformation that isanalogous to that observed for [Ln(₂-P₂W₁₇O₆₁)₂]^17- but with"empty" O₄ tetrahedra that are in positions remote from the ceriumatom. Bond valence sum calculations for these structures showthat the four protons that are required for charge balance in allsalts of the XW₁₈ anions and their lacunary derivatives are almostcertainly bound to the oxygen atoms of the empty tetrahedra.