4.8 Article

[Sn8]6--Bridged Mixed-Valence ZnI/ZnII in {[K2ZnSn8(ZnMes)]2}4- Inverse Sandwich-Type Cluster Supported by a ZnI-ZnI Bond

期刊

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 18, 页码 9990-9995

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202102578

关键词

Sn8](6-); inverse sandwich; local s-aromaticity; mixed valence ZnI/ZnII; Zn-Zn bond

资金

  1. National Natural Science Foundation of China [21971118]
  2. USA National Science Foundation [CHE-1664379]
  3. R. Gaurth Hansen Professorship fund
  4. Centre for High Performance Computing at the University of Utah
  5. FONDECYT [1180683]

向作者/读者索取更多资源

In this study, an inverse sandwich-type cluster dimer was synthesized and characterized, in which the highly charged [Sn-8](6-) is captured by mixed-valence Zn-I/Zn-II. Theoretical calculations indicate that the delocalization of electrons over Zn atoms plays a vital role in the stabilization of the [Sn-8](6-) species.
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 {[K2ZnSn8(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-[Zn2Sn8]}(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 eta(4):eta(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 sigma-aromaticity in three cluster fragments: two ZnSn4 caps and Sn-8 square antiprism.

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