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Chemistry

The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique

Published: November 28th, 2016

DOI:

10.3791/54498

1Chemistry Department, Institute of Inorganic Chemistry, University of Tübingen

The disproportionation reaction of a metastable Sn(I) chloride solution, obtained via the preparative co-condensation technique, is used for the synthesis of a metalloid tin cluster compound.

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a sterically demanding ligand, has increased in recent years. The metastable Sn(I) halide is synthesized at "outer space conditions" via the preparative co-condensation technique. Thereby, the subhalide is synthesized in an oven at high temperatures, around 1,300 °C, and at reduced pressure by the reaction of elemental tin with hydrogen halide gas (e.g., HCl). The subhalide (e.g., SnCl) is trapped within a matrix of an inert solvent, like toluene at -196 °C. Heating the solid matrix to -78 °C gives a metastable solution of the subhalide. The metastable subhalide solution is highly reactive but can be stored at -78 °C for several weeks. On heating the solution to room temperature, a disproportionation reaction occurs, leading to elemental tin and the corresponding dihalide. By applying bulky ligands like Si(SiMe3)3, the intermediate metalloid cluster compounds can be trapped before complete disproportionation to elemental tin. Hence, the reaction of a metastable Sn(I)Cl solution with Li-Si(SiMe3)3 gives [Sn10(Si(SiMe3)3)4]2- 1 as black crystals in high yield. 1 is formed via a complex reaction sequence including salt metathesis, disproportionation, and degradation of larger clusters. Further, 1 can be analyzed by various methods like NMR or single crystal X-ray structure analysis.

Due to recent progress in the field of nanotechnology, the nanoscale size range between molecules and the solid state became more and more important and is the focus of various research efforts1. Research with nanoscaled compounds is especially of interest for metals or semimetals, as drastic changes take place during the transformation from small molecular species (e.g., oxides, halides: non-conducting; e.g., AlCl3, AuCl3, GeO2, etc.) to metalloid clusters2 of the general formulae MnRm (n>m; M = metal such as Al, Au, Sn, etc.; R = ligand such as S....

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CAUTION! Please consult all relevant material safety data sheets (MSDS) before use. Several of the chemicals used in these syntheses are acutely toxic, pyrophoric, and carcinogenic. Nanomaterials may have additional hazards compared to their bulk counterpart. Please use all appropriate safety practices when performing a reaction, including the use of engineering controls (fume hood and glovebox) and personal protective equipment (safety glasses, gloves, lab coat, full length pants, and closed-toe shoes)........

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The principle of the matrix isolation technique in conjugation with the preparative co-condensation technique is shown (Figure 1), as well as the setup of the co-condensation apparatus (Figure 2) and the graphite reactor (Figure 3). Figures 4 and 5 show photos of the assembly of the co-condensation apparatus. In Figure 6, the gas supply components with the mass flow controller are shown. .......

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By applying the preparative co-condensation technique (Figure 1)25, novel materials based on molecules like SnBr are obtained. Due to the high flexibility in temperature, pressure, metal, and reactive gas, a large variety of metastable solutions of high reactive species can be synthesized. For example, subhalides of silicon and germanium are already obtained in this way. However, finding the right conditions to obtain a metastable solution for further synthesis is not trivial, and the solution.......

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We are grateful to the Deutsche Forschungsgemeinschaft (DFG) for financial support, and we thank Dr. Daniel Werner for helpful discussions.

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Name Company Catalog Number Comments
Tin 99.999% ABCR AB122397
HydrogenchlorideN28  99.8% Air Liquide P0820S10R0A001 Toxic
Toluene anhydrous 99.8% Sigma Aldrich 244511
Tri-n-butylphosphine >93.5% Sigma Aldrich 90827 Toxic
TMEDA, >99.5% Sigma Aldrich 411019
12-crown-4 Sigma Aldrich 194905 Toxic
THF anhydrous, >99.9% Sigma Aldrich 401757
Sodium, 99.95% Sigma Aldrich 262715
Benzophenone, >99% Sigma Aldrich 427551
Differential pressure manometer  MKS MKS Baratron 223B
Mass flow controller  Bronckhorst  Low Δp flow mass flow controller
High frequency generator Trumpf Hüttinger TruHeat MF 5020
NMR spectrometer Bruker Bruker DRX-250
Glovebox GS Systemtechnik
Argon 5.0 Westfalen
Nitrogen 4.8 Westfalen
Graphite SGL
Quartz glass tube Gebr. Rettberg GmbH
Steel transferring cannula Rohre Ketterer
Balance Kern Kern PFB200-3
Oil diffusion pump Balzers Balzers Diff900
Rotary vane pump Balzers Balzers QK100L4D
Pyrometer Sensotherm 6285
Schlenk tubes with glassy stopcocks Gebr. Rettberg GmbH J.-Young-type valve with glassy stopcock

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