Rational Synthesis and Characterization of the Mixed-Metal Organometallic Polyoxometalates [Cp*MoxW6鈥?i>xO18]鈭?/sup> (x = 0, 1, 5, 6)

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• 作者：G眉lnur Taban-脟al谋艧kan ; Daniel Mesquita Fernandes ; Jean-Claude Daran ; Dominique Agustin ; Funda Demirhan ; Rinaldo Poli
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：May 21, 2012
• 年：2012
• 卷：51
• 期：10
• 页码：5931-5940
• 全文大小：410K
• 年卷期：v.51,no.10(May 21, 2012)
• ISSN：1520-510X

文摘

The reaction between the oxometallic complexes Cp*₂M₂O₅ and Na₂M鈥睴₄ (M, M鈥?= Mo, W) in a 1:10 molar ratio in an acidic aqueous medium constitutes a mild and selective entry into the anionic Lindqvist-type hexametallic organometallic mixed oxides [Cp*Mo_xW_6鈥?i>xO₁₈]^{鈭?/sup> [x = 6 (1), 5 (2), 1 (3), 0 (4)]. All of these compounds have been isolated as salts of nBu₄N+ (a), nBu₄P+ (b), and Ph₄P+ (c) cations and two of them (1 and 3) also with the n-butylpyridinium (nBuPyr+, d) cation. The compounds have been characterized by elemental analyses, thermogravimetric analyses, electrospray mass spectrometry, and IR spectroscopy. The molecular identity and geometry of compounds 1c, 2a, and 2c have been confirmed by single-crystal X-ray diffraction. Density functional theory calculations on models obtained by replacing Cp* with Cp (I鈥?b>IV) have provided information on the assignment of the terminal M鈺怬 and bridging M鈥揙鈥揗 vibrations.}