[Cu₁₃{S₂CNⁿBu₂}₆(acetylide)₄]⁺: A Two-Electron Superatom

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• 作者：Dr. Kiran Kumarvarma Chakrahari ; Jian-Hong Liao ; Dr. Samia Kahlal ; Dr. Yu-Chiao Liu ; Dr. Ming-Hsi Chiang ; Prof. Jean-Yves Saillard and Prof. C. W. Liu
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：November 14, 2016
• 年：2016
• 卷：128
• 期：47
• 页码：14924-14928
• 全文大小：1763K
• ISSN：1521-3757

文摘

The first structurally characterized copper cluster with a Cu₁₃ centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu₁₃(S₂CNⁿBu₂)₆(C≡CR)₄](PF₆) (R=C(O)OMe, C₆H₄F) nanoclusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in μ₃ fashion, and each of the six square faces is bridged by a dithiolate ligand in μ₂,μ₂ fashion, which leads to a truncated tetrahedron of twelve sulfur atoms. DFT calculations are fully consistent with the description of these Cu₁₃ clusters as two-electron superatoms, that is, a [Cu₁₃]¹¹⁺ core passivated by ten monoanionic ligands, with an a₁ HOMO containing two 1S jellium electrons.