Since [Sn ] 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 ZnSn (ZnMes)] } (1 a), in which the highly charged [Sn ] is captured by mixed-valence Zn /Zn to form the dimer {closo-[Zn Sn ]} moieties bridged by a Zn-Zn bond. Such Zn-Sn cluster not only exhibits a novel example of mixed-valence Zn /Zn for stabilizing highly active anion species, but also indicates the [Sn ] cluster can act as a novel bridging ligand, like arene, with a η :η -fashion. Theoretical calculations indicate that a significant delocalization of electrons over Zn atoms plays a vital role in the stabilization of the [Sn ] species. The AdNDP and magnetic response analyses clearly showed the presence of local σ-aromaticity in three cluster fragments: two ZnSn caps and Sn square antiprism.
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