Acidobasic behavior of the diphosphato dodecameric ring [(HPO₄)₂Mo₁₂S₁₂O₁₂(OH)₁₂(H₂O)₂]⁴⁻. Synt

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• 作者：Cadot ; Emmanuel ; Salignac ; Bernadette ; Marrot ; Jé ; rô ; me ; Sé ; cheresse ; Francis
• 关键词：Polyoxometalate ; Thiometalate ; Molybdenum ; Inorganic cycle
• 刊名：Inorganica Chimica Acta
• 出版年：2003
• 出版时间：July 4, 2003
• 年：2003
• 卷：350
• 期：Complete
• 页码：414-420
• 全文大小：349 K

文摘

A novel diphosphato anionic ring, [(HPO₄)₂Mo₁₂S₁₂O₁₂(OH)₁₄(H₂O)₂]⁶⁻ noted B-[P₂Mo₁₂]⁶⁻ was characterized by single crystal-X ray diffraction. B-[P₂Mo₁₂]⁶⁻ formally derives from the acidic parent [(HPO₄)₂Mo₁₂S₁₂O₁₂(OH)₁₂(H₂O)₂]⁴⁻ (noted A-[P₂Mo₁₂]⁴⁻) by addition of two hydroxo groups in the cavity. The phosphate groups are hydrogen bonded to the inner hydroxo bridges. The H-bonding network within the cavity contributes to the elliptical conformations which differ in the acid and basic conjugated forms. The basic B-[P₂Mo₁₂]⁶⁻ ring was characterized in solution by ³¹P NMR. The three-line spectrum indicates that a chemical equilibrium takes place for giving uncoordinated phosphate and a monophosphate ring, noted [PMo₁₀]ⁿ⁻. IR characterizations are also given.