Peculiar All‐Metal σ‐Aromaticity of the [Au2Sb16]4− Anion in the Solid State |
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| Authors: | 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 Prof. Dr. Alexander I. Boldyrev |
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| Affiliation: | 1. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Jilin, China;2. Department of Chemistry and Biochemistry, Utah State University, Logan, UT, USA;3. Shanxi University, Institute of Molecular Science, Taiyuan, China;4. Euskal Herriko Unibertsitatea (UPV/EHU) Donostia International Physics Center (DIPC), Euskadi, Spain;5. IKERBASQUE Basque Foundation for Science, Bilbao, Spain;6. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, China |
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| Abstract: | 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. |
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| Keywords: | all-metal compounds aromaticity chemical bonding structure elucidation Zintl anions |
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