[Cu13{S2CNnBu2}6(acetylide)4]+: A Two-Electron Superatom
[Cu13{S2CNnBu2}6(acetylide)4]+: A Two-Electron Superatom
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DOI：
10.1002/anie.201608609
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发表时间：
2016-11-14
影响因子：
16.6
通讯作者：
Liu, C. W.
中科院分区：
文献类型：
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作者：
Chakrahari, Kiran Kumarvarma;Liao, Jian-Hong;Liu, C. W.
在[Cu-13（（S_2CNBu_2）-Bu-n）（6）（CR）（4）]（PF_6）（R = C（O）OMe，C_6H_4F）纳米团簇中，首次观察到了具有Cu-13为中心的立方八面体结构的铜团簇，这是铜的体相fcc结构的模型.立方八面体的八个三角形面中的四个以mu（3）方式被乙炔基封端，六个正方形面中的每一个以mu（2），mu（2）方式被二硫醚配体桥接，这导致十二个硫原子的截短四面体。DFT计算结果与Cu-13团簇的双电子超原子描述完全一致，即[Cu-13]（11+）核被10个单阴离子配体钝化，其中a（1）HOMO含有两个1 S jelvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvonic-elvon-elvonic-elvonic-elvon-elvon-elvonic-elvon-elvon-elvon-elvon-elvon-elvonicon-elvon-elvon-elvon-elvonicon-elvon-elvon-elvon-el
The first structurally characterized copper cluster with a Cu-13 centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu-13((S2CNBu2)-Bu-n)(6)(C CR)(4)](PF6) (R = C(O)OMe, C6H4F) nano-clusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in mu(3) fashion, and each of the six square faces is bridged by a dithiolate ligand in mu(2),mu(2) fashion, which leads to a truncated tetrahedron of twelve sulfur atoms. DFT calculations are fully consistent with the description of these Cu-13 clusters as two-electron superatoms, that is, a [Cu-13](11+) core passivated by ten monoanionic ligands, with an a(1) HOMO containing two 1S jellium electrons.