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Biologie

ゲルマニウムと有機基との官能の9原子Deltahedral Zintlイオンの合成

Published: February 11, 2012
doi:
10.3791/3532
,
1Department of Chemistry and Biochemistry,University of Notre Dame

Summary

我々は、金属前駆体Kの高温合成を提示<sub> 4</sub> GE<sub> 9</sub>は、Geを形成するために、エチレンジアミンでの解散<sub> 9</sub<sup> 4 -</sup> deltahedral Zintlイオン、有機Zintlイオンを形成するために、アルキンとクラスターの反応。後者は溶液中のエレクトロスプレー質量分析により、固体状態での単結晶X線回折によって特徴付けられる。

Abstract

1890年代後半と1930年代初期の間にZintlイオンの日付の最初の研究が、多くの年後まで、それらは構造的に特徴付けされていません。1,2彼らの酸化還元化学だけで約10歳も年下ですが、この短い歴史にもかかわらず、これらのdeltahedralクラスターイオンE 9 N-（E =は、Si、Ge、Snの鉛であり、n = 2、3、4）は、すでに興味深い多様な反応性を示していると急速に発展し、エキサイティングな新しい化学の最前線にされている3月6日注目すべきマイルストーンがあります。 Geの9 4の酸化カップリング–オリゴマーと無限チェーンにクラスタ、7月19日彼らのメタル化、遷移金属有機金属フラグメントの中心に遷移金属原子の26から34を挿入することによりキャッピング14-16,20-25時にはキャッピングとオリゴマーと結合されるクラスタでは、エキソ-結合置換基としてメイングループ有機金属フラグメントの35から47に加え、有機ハロゲン化物とアルキンとの反応により、種々の有機残基48から50と官能。51から58

クラスタに直接有機フラグメントをアタッチするこの後者の開発は、さらに合成の探求のために潜在的に肥沃で、新しいフィールド、すなわち有機Zintl化学を、開かれている、それはゲルマニウム – ジビニルの合成のためのステップバイステップの手順です。クラスタは、本明細書に記載。最初の手順は、Ge Geの9 9 4からK 4の金属間化合物前駆体の合成の概要を説明–クラスタは、後の溶液中で抽出されます。これは、フューズドシリカガラス、ニオブ容器のアーク溶接を吹いて、グローブボックス内での高い空気に敏感な材料の取り扱いを伴います。空気が敏感なK 4 Geの9は、その後のボックスにエチレンジアミンに溶解し、次いでミー3のSiC≡CSiMe 3との反応によってアルケニルされています。反応は、電気が続いているエレクトロスプレー質量分析得られた溶液は、官能クラスター[H 2 C = CH-GE 9-CH = CH 2] 2を含有する単結晶を得るために使用されている間に– 。この目的のために溶液は、遠心分離、濾過し、慎重に18 – クラウン-6のトルエン溶液と階層化されています。数日間静置ので、多層ソリューションは、オレンジ色の結晶性ブロック[K（18 -クラウン-6）] 2 [GE 9（HCCH 2）2]を生成する•EN単結晶X線回折によって特徴付けされた。

プロセスは、標準的な反応技術、後処理、および官能deltahedral Zintlクラスタに対する解析を強調しています。それが大規模で社会におけるこれらの化合物のさらなる発展と理解に向けて役立つことが期待されている。

Protocol

1。ニオブ管を準備するニオブ（Nb）のチューブを切断する前には、Nb-洗浄液を準備します。 500ミリリットルペットボトルでは、外を測定し、受信したとして、次のストック溶液をメスシリンダー100ミリリットルを経由して追加します。110ミリリットルH 2 SO 4、40ミリリットルHFに続いて50ミリリットルHNO 3、続いて。よく混ぜて使用する前に室温に達することが…

Discussion

それも部分的に酸化ニオブ管をきれいにすることが重要です。チューブが長すぎるNbの洗浄溶液中で残っている場合は、これは深刻なチューブの厚さが損なわれます。したがって、10から15秒が不可欠であり、チューブの端（図3）で非常に光沢がでなければなりません。管は石英ガラスジャケット内に封入された後、それらが希薄なニオブ酸溶液で再洗浄する必要があります。これは、溶接や…

Divulgations

The authors have nothing to disclose.

Acknowledgements

著者らは、連続的な財政支援（CHE-0742365）、およびブルカーAPEX II回折（CHE-0443233）とブルカーMicrotof-II質量分析計（CHE-0741793）を購入するための国立科学財団（NSF）に感謝します。また、作者はMicromass社クアトロ-LC質量分析計の利用のためにCEST施設に感謝します。

Materials

Name of the reagent Company Catalogue number Comments
D8-Xray diffractometer Bruker Bruker APEX II  
Electrospray mass spectrometer Bruker Microtof-II  
Electrospray mass spectrometer Micromass Quattro-LC triple -quadropole
Drybox Innovative Technology S-1-M-DL IT-Sys1 model
Inert Gas/Vacuum Shielded
Arc Welding Arrangement		 LDS Vacuum Products Special Order
Arc Welder Power Source Miller Maxstar-91  
Welding Rubber Gloves The Home Depot  KH643  
Electric Engraver Burgess Products 74 Vibro-Graver
Circular Glass Saw Pistorius Machine Co. Inc GC-12-B  
Tube Furnace Lindberg/Blue M TF55035 Minimite Laboratory Tube Furnace, Moldatherm (1100 °C)
Glass Drying Oven Fisher Scientific 13-247-650G  
High Vacuum Hg Schlenk-Line Special Order Univ Of Notre Dame Alternative: Edwards E050/60; VWR International; Cat. No. EVB302-07-110
Large Torch Victor JT100C Welding torch, tip: Victor 5-W-J
Small Torch Veriflo Co. 3A Blow-pipe
Tesla Coil VWR International KT691550-0000 Leak detector
Stirrer/Hot -Plate VWR International 12620-970 VWR HOT PLATE STR DY-DUAL120V
Balance Denver Instrument Co. 100A XE Series
Centrifuge LW Scientific E8C-08AV-1501 Variable speed
Graphite Reamer, (flaring) ABR Imagery, Inc. 850-523 B01 Open holes in Glass Blowing and flaring edges
Striker Fisher Scientific 12-007  
Vise-Grips The Home Depot 0902L3SM  
Pipe-Cutter The Home Depot 32820  
Cutting Pliers The Home Depot 437  
Plastic Beaker VWR International 13890-046  
Measuring Cylinder VWR International 65000-006 Careful, HF etches glass (if using a glass one)
Large Plastic Bottle VWR International 16128-542  
13 x 100 Test-Tubes VWR International 47729-572 CULTURE TUBE 13X100 CS1000
Laboratory (Rubber) Stoppers Sigma Chemical Co. Z164437-100EA Size 00
Test-Tube Rack VWR International 60196-702 10-13 mm tube OD
Stir-Bars StirBars.com/Big Science Inc. SBM-0803-MIC PTFE 8×3 mm Micro
Glass Pipettes VWR International 14673-043 VWR PIPET PASTEUR 9IN CS1000
Rubber Bulbs VWR International 56311-062 Latex, thin walled
Glass Wool Unifrax I LLC 6048 Fiberfrax Bulk Fiber Insulation, Ceramic fiber
Glass Slides VWR International 16004-422 75x25x1mm, Microscope Slides
Paratone-N oil Hampton Research Parabar 10312 Known as: Paratone-N, Paratone-8277, Infineum V8512
High Vacuum Silicone Grease VWR International 59344-055 Dow Corning
Liquid Nitrogen Univ. of Notre Dame    
Argon Gas Cylinder Praxair Distribution Inc. TARGHP  
Nitrogen Gas Cylinder Praxair Distribution Inc. QNITPP  
Oxygen Gas Cylinder Praxair Distribution Inc. OT 337 cf CYL
Hydrogen Gas Cylinder Praxair Distribution Inc. HK 195 cf CYL
Propane Gas Cylinder/source Univ. of Notre Dame UND  
Quartz tubing, Lg Quartz Scientific Inc. 100020B 20 mm id x 22mm od x 48″ clear fused quart tubing
Quartz tubing, Md Quartz Scientific Inc. 100007B Clear Fused Quartz Tubing,7mm id x 9mm od x 48″
Round Bottom Quartz Joint Quartz Scientific Inc. 6160189B Ball joint
Quartz Safety Glasses Wale Apparatus 11-1127 waleapparatus.com
Pyrex Safety Glasses Wale Apparatus 11-2125-B3 For clear and color borosilicate glass
Blow Hose Kit Glass House BH020 glasshousesupply.com
Niobium Tubes Shaanxi Tony Metals Co., Ltd Niobium Tube, 50 ft Seamless Niobium Tube Outside diameter: 0.375 (±0.005) inches.
Wall thickness: 0.02(±0.003) Inches Niobium should be annealed.
PEEK Starter Kit for Mass Spect Waters PSL613321 PEEK (PolyEtherEtherKetone) tubing, nuts, ferrule, fits
Mass Spect Needle Set VWR International 60373-992 Hamilton Manufacturer (81165)
H2SO4 VWR International BDH3072-2.5LG ACS Grade
HNO3 VWR International BDH3046-2.5LPC ACS Grade
HF VWR International BDH3040-500MLP ACS Grade
Distilled Water Univ. of Notre Dame UND  
Acetone VWR International BDH1101-4LP  
Ethylenediamine VWR International AAA12132-0F 99% 2.5 L
Toluene VWR International 200004-418 99.8 %, anhydrous
Mercury Strem Chemicals, Inc. 93-8046  
Potassium (K) metal Strem Chemicals, Inc. 19-1989 Sealed in glass ampoule under Ar
Germanium (Ge) powder VWR International AA10190-18 GERM PWR -100 MESH 99.999% 50G
Bistrimetylsilylacetylene,
(Me3SiC≡CCSiMe3)		 Fischer Scientific AC182010100  
18-crown-6
(1,4,7,10,13,16-Hexaoxacyclooctadecane)		 VWR International 200001-954 99%, 25 gm
2,2,2-crypt
(4,7,13,16,21,24-Hexaoxa-1,10 diazabicyclo[8.8.8]hexacosane)		 Sigma Aldrich 291110-1G 98%
DOWNLOAD MATERIALS LIST

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Tags

Zintl IonsGermaniumFunctionalizationOrganic GroupsRedox ChemistryDeltahedral ClustersReactivityChimieClusters SynthesisGermanium-divinyl Clusters
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Gillett-Kunnath, M. M., Sevov, S. C. Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups. J. Vis. Exp. (60), e3532, doi:10.3791/3532 (2012).
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