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Peculiar All‐Metal σ‐Aromaticity of the [Au 2 Sb 16 ] 4− Anion in the Solid State
Author(s) -
Popov Ivan A.,
Pan FuXing,
You XueRui,
Li LeiJiao,
Matito Eduard,
Liu Chao,
Zhai HuaJin,
Sun ZhongMing,
Boldyrev Alexander I.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201609497
Subject(s) - aromaticity , delocalized electron , chemistry , cluster (spacecraft) , crystallography , electron , ion , metal , chemical physics , electron counting , electron delocalization , molecule , physics , organic chemistry , quantum mechanics , computer science , programming language
Gas‐phase clusters are deemed to be σ‐aromatic when they satisfy the 4 n +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 [Au 2 Sb 16 ] 4− cluster core possessing two all‐metal aromatic AuSb 4 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.