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[Sn 8 ] 6− ‐Bridged Mixed‐Valence Zn I /Zn II in {[K 2 ZnSn 8 (ZnMes)] 2 } 4− Inverse Sandwich‐Type Cluster Supported by a Zn I −Zn I Bond
Author(s) -
Xu HongLei,
Tkachenko Nikolay V.,
MuñozCastro Alvaro,
Boldyrev Alexander I.,
Sun ZhongMing
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202102578
Subject(s) - crystallography , delocalized electron , chemistry , square antiprism , valence (chemistry) , dimer , cluster (spacecraft) , valence electron , ion , inorganic chemistry , electron , lanthanide , physics , computer science , programming language , organic chemistry , quantum mechanics
Since [Sn 8 ] 6− was discovered from the solid‐state phase in 2000, its solution chemistry has been elusive due to the high charges and chemical activity. Herein, we report the synthesis and characterization of an inverse sandwich‐type cluster dimer {[K 2 ZnSn 8 (ZnMes)] 2 } 4− ( 1 a ), in which the highly charged [Sn 8 ] 6− is captured by mixed‐valence Zn I /Zn II to form the dimer { closo ‐[Zn 2 Sn 8 ]} 2 moieties bridged by a Zn‐Zn bond. Such Zn‐Sn cluster not only exhibits a novel example of mixed‐valence Zn I /Zn II for stabilizing highly active anion species, but also indicates the [Sn 8 ] 6− cluster can act as a novel bridging ligand, like arene, with a η 4 :η 4 ‐fashion. Theoretical calculations indicate that a significant delocalization of electrons over Zn atoms plays a vital role in the stabilization of the [Sn 8 ] 6− species. The AdNDP and magnetic response analyses clearly showed the presence of local σ‐aromaticity in three cluster fragments: two ZnSn 4 caps and Sn 8 square antiprism.