Comproportionation Synthesis of Copper(I) Alkynyl Complexes Encapsulating Polyoxomolybdate Templates: Bowl-Shaped Cu33 and Peanut-Shaped Cu62 Nanoclusters

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• 作者：Li-Min Zhang ; Thomas C. W. Mak
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：March 9, 2016
• 年：2016
• 卷：138
• 期：9
• 页码：2909-2912
• 全文大小：297K
• ISSN：1520-5126

文摘

Comproportionation reaction of Cu(II) salt and copper metallic powder in the presence of tert-butylacetylene (tBuC≡CH) in methanol at room temperature yielded discrete Cu(I) tert-butylethynide clusters whose identity depended on the particular co-existing anion employed. Introduction of polyoxomolybdate to the reaction system afforded two new core–shell nanoclusters, [Cu₃₃(tBuC≡C)₂₄(Mo₄O₁₆)]·BF₄ (3) and [Cu₆₂(tBuC≡C)₃₄(Mo₅O₁₉)₂(MoO₄)₂(OTf)₂(OH)₄]·(OTf)₂ (4). Complexes 3 and 4 represent the first examples of high-nuclearity Cu(I) clusters that encapsulate polyoxometalate templates, and the latter features the largest Cu(I) alkynyl cluster known to date. The present study not only demonstrates a new paradigm for the designed synthesis of Cu(I) alkynyl clusters but also opens the door to understanding Cu(I) alkynyl structural chemistry.