An Approach to the Synthesis of Polyoxometalate Encapsulating Different Kinds of Oxoanions as Heteroions: Bisphosphitopyrophosphatotriacontamolybdate [(HPO3)2(P2O

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• 作者：Sayuri Maeda ; Takuya Goto ; Masayo Takamoto ; Kazuo Eda ; Sadayuki Himeno ; Hiroki Takahashi ; Toshitaka Hori
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：December 1, 2008
• 年：2008
• 卷：47
• 期：23
• 页码：11197-11201
• 全文大小：201K
• 年卷期：v.47,no.23(December 1, 2008)
• ISSN：1520-510X

文摘

A yellow [(HPO₃)₂(P₂O₇)Mo₃₀O₉₀]⁸⁻ anion was prepared as a tetrapropylammonium (Pr₄N⁺) salt from a 50 mM Mo^VI−2 mM P₂O₇⁴⁻−4 mM HPO₃²⁻−0.95 M HCl−60% (v/v) CH₃CN system at ambient temperature. The (Pr₄N)₈[(HPO₃)₂(P₂O₇)Mo₃₀O₉₀] salt crystallized in the orthorhombic space group P_nma (No. 62), with a = 30.827(2) Å, b = 22.8060(15) Å, c = 30.928(2) Å, V = 21743(3) ų, and Z = 4. The structure contained a (P₂O₇)Mo₁₂O₄₂ fragment derived from the removal of each corner-shared Mo₃O₁₃ unit in a polar position from a [(P₂O₇)Mo₁₈O₅₄]⁴⁻ structure, and each side of the (P₂O₇)Mo₁₂O₄₂ fragment was capped by a B-type (HPO₃)Mo₉O₂₄ unit. The [(HPO₃)₂(P₂O₇)Mo₃₀O₉₀]⁸⁻ anion was characterized by voltammetry and IR, UV−vis, and ³¹P NMR spectroscopy. Unlike the Keggin and Dawson anions and the parent [(P₂O₇)Mo₁₈O₅₄]⁴⁻ anion, the [(HPO₃)₂(P₂O₇)Mo₃₀O₉₀]⁸⁻ anion exhibited two-electron redox waves in CH₃CN with and without acid.