[Sn8]6--Bridged Mixed-Valence ZnI/ZnII in {[K2ZnSn8(ZnMes)]2}4− Inverse Sandwich-Type Cluster Supported by a ZnI−ZnI Bond
Document Type
Article
Journal/Book Title
Angewandte Chemie International Edition
Publication Date
3-7-2021
Publisher
Wiley-VCH Verlag GmbH & Co. KGaA
Award Number
NSF, Division of Chemistry (CHE) 1664379
Funder
NSF, Division of Chemistry (CHE)
Volume
60
Issue
18
First Page
9990
Last Page
9995
Abstract
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 {[K2ZnSn8(ZnMes)]2}4− (1 a), in which the highly charged [Sn8]6− is captured by mixed-valence ZnI/ZnII to form the dimer {closo-[Zn2Sn8]}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.
Recommended Citation
H.-L. Xu, N. V. Tkachenko, A. Muñoz-Castro, A. I. Boldyrev, Z.-M. Sun, Angew. Chem. Int. Ed. 2021, 60, 9990.
