Peculiar All-Metal σ-Aromaticity of the [Au₂Sb₁₆]⁴⁻ Anion in the Solid State

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• 作者：Ivan A. Popov ; Fu-Xing Pan ; Xue-Rui You ; Dr. Lei-Jiao Li ; Dr. Eduard Matito ; Chao Liu ; Prof. Dr. Hua-Jin Zhai ; Prof. Dr. Zhong-Ming Sun and Prof. Dr. Alexander I. Boldyrev
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：December 5, 2016
• 年：2016
• 卷：55
• 期：49
• 页码：15344-15346
• 全文大小：1209K
• ISSN：1521-3773

文摘

Gas-phase clusters are deemed to be σ-aromatic when they satisfy the 4n+2 rule of aromaticity for delocalized σ electrons and fulfill other requirements known for aromatic systems. While the range of n values was shown to be quite broad when applied to short-lived clusters found in molecular-beam experiments, stability of all-metal cluster-like fragments isolated in condensed phase was previously shown to be mainly ascribed to two electrons (n=0). In this work, the applicability of this concept is extended towards solid-state compounds by demonstrating a unique example of a storable compound, which was isolated as a stable [K([2.2.2]crypt)]⁺ salt, featuring a [Au₂Sb₁₆]⁴⁻ cluster core possessing two all-metal aromatic AuSb₄ fragments with six delocalized σ electrons each (n=1). This discovery pushes the boundaries of the original idea of Kekulé and firmly establishes the usefulness of the σ-aromaticity concept as a general idea for both small clusters and solid-state compounds.