Synthesis, Structure, and Electrochemistry of the Ni鈥揂u Carbonyl Cluster [Ni12Au(CO)24]3鈥?/sup> and Its Relation to [Ni32Au6(CO)44]6鈥?/

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• 作者：Iacopo Ciabatti ; Cristina Femoni ; Maria Carmela Iapalucci ; Giuliano Longoni ; Stefano Zacchini ; Serena Fedi ; Fabrizia Fabrizi de Biani
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：November 5, 2012
• 年：2012
• 卷：51
• 期：21
• 页码：11753-11761
• 全文大小：457K
• 年卷期：v.51,no.21(November 5, 2012)
• ISSN：1520-510X

文摘

A detailed study of the reaction between [Ni₆(CO)₁₂]^{2鈥?/sup> and [AuCl₄]鈭?/sup> afforded the isolation of the new Ni鈥揂u cluster [Ni₁₂Au(CO)₂₄]3鈥?/sup> as well as identifying an improved synthesis for the previously reported [Ni₃₂Au₆(CO)₄₄]6鈥?/sup>. The new [Ni₁₂Au(CO)₂₄]3鈥?/sup> cluster is composed by two [Ni₆(CO)₁₂]2鈥?/sup> moieties coordinated to a central Au(I) ion, as determined by X-ray diffraction. It is noteworthy that the two [Ni₆(CO)₁₂]2鈥?/sup> fragments display different geometries, i.e., trigonal antiprismatic (distorted octahedral) and distorted trigonal prismatic (monocapped square pyramidal). The chemical reactivity of these clusters and their electrochemical behavior have been studied. [Ni₁₂Au(CO)₂₄]3鈥?/sup> is irreversibly transformed, upon electrochemical reduction, into Au(0) and [Ni₆(CO)₁₂]2鈥?/sup>, followed by the reversible reduction of the latter homometallic cluster. Conversely, [Ni₃₂Au₆(CO)₄₄]6鈥?/sup> displays five reductions, with apparent features of reversibility, confirming the ability of larger metal carbonyl clusters to reversibly accept and release electrons.}