LiGe(SiMe₃)₃: A New Substituent for the Synthesis of Metalloid Tin Clusters from Metastable Sn(I) Halide Solutions.

Mareike Binder,Andreas Schnepf,Theresa Block,Claudio Schrenk,Rainer Pöttgen

doi:10.3390/molecules23051022

Mareike Binder, Andreas Schnepf + Show 3 more

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https://doi.org/10.3390/molecules23051022

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Abstract

The most fruitful synthetic route to metalloid tin clusters applies the disproportionation reaction of metastable Sn(I) halide solutions, whereby Si(SiMe3)3 is mostly used as the stabilizing substituent. Here, we describe the synthesis and application of the slightly modified substituent Ge(SiMe3)3, which can be used for the synthesis of metalloid tin clusters to give the neutral cluster Sn10[Ge(SiMe3)3]6 as well as the charged clusters {Sn10[Ge(SiMe3)3]5}− and {Sn10[Ge(SiMe3)3]4}2−. The obtained metalloid clusters are structurally similar to their Si(SiMe3)3 derivatives. However, differences with respect to the stability in solution are observed. Additionally, a different electronic situation for the tin atoms is realized as shown by 119mSn Mössbauer spectroscopy, giving further insight into the different kinds of tin atoms within the metalloid cluster {Sn10[Ge(SiMe3)3]4}2−. The synthesis of diverse derivatives gives the opportunity to check the influence of the substituent for further investigations of metalloid tin cluster compounds.

Highlights

In the last couple of years, the developments in nanotechnology as well as their industrial applications have generated interest in nanoscaled molecular materials [1]
The germanide [Ge(SiMe3 )3 ]− is synthesized by a similar synthetic route to that of the (Hyp) substituent [23]
After the successful synthesis of LiGe(SiMe3 )3, it was necessary to check if LiGe(SiMe3 )3 can be used for the synthesis of metalloid tin clusters via the disproportionation reaction of a metastable Sn(I) halide solution

Summary

Introduction

In the last couple of years, the developments in nanotechnology as well as their industrial applications have generated interest in nanoscaled molecular materials [1]. One example of such nanoscaled compounds is the group of metalloid clusters of the general formula Mn Rm (n > m; M = Al, Ga, Sn, Pb, Au, etc.; R = N(SiMe3 ) , Si(SiMe3 ) , etc.) [2]. In the case of metalloid cluster compounds of tin, we introduced a special synthetic route, applying the disproportionation reaction of a metastable SnI halide solution [6,7]. Thereby, a SnI halide is condensed together with a mixture of an organic solvent and a donor component such as PnBu3 at −196 ◦ C

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