[Sn8 ]6- -Bridged Mixed-Valence ZnI /ZnII in {[K2 ZnSn8 (ZnMes)]2 }4- Inverse Sandwich-Type Cluster Supported by a ZnI -ZnI Bond.

Since [Sn8 ]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 {[K2 ZnSn8 (ZnMes)]2 }4- (1 a), in which the highly charged [Sn8 ]6- is captured by mixed-valence ZnI /ZnII to form the dimer {closo-[Zn2 Sn8 ]}2 moieties bridged by a Zn-Zn bond. Such Zn-Sn cluster not only exhibits a novel example of mixed-valence ZnI /ZnII for stabilizing highly active anion species, but also indicates the [Sn8 ]6- cluster can act as a novel bridging ligand, like arene, with a η4 :η4 -fashion. Theoretical calculations indicate that a significant delocalization of electrons over Zn atoms plays a vital role in the stabilization of the [Sn8 ]6- species. The AdNDP and magnetic response analyses clearly showed the presence of local σ-aromaticity in three cluster fragments: two ZnSn4 caps and Sn8 square antiprism.