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Summary
Abstract
Protocol
Discussion
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Acknowledgements
Materials
References
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Biology

नौ परमाणु जर्मेनियम की Deltahedral Zintl आयनों और उनके functionalization की कार्बनिक समूह के साथ संश्लेषण

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

Summary

हम उच्च तापमान intermetallic व्यापारियों की कश्मीर संश्लेषण प्रस्तुत<sub> 4</sub> जीई<sub9></sub> Ethylenediamine में उनके विघटन जीई फार्म<sub9></sub<sup> 4 -</sup> Deltahedral Zintl आयनों, और alkynes साथ समूहों की प्रतिक्रिया organo Zintl आयनों के रूप में. बाद electrospray समाधान में मास स्पेक्ट्रोमेट्री और ठोस राज्य में एकल क्रिस्टल एक्स – रे विवर्तन द्वारा विशेषता है.

Abstract

Although the first studies of Zintl ions date between the late 1890’s and early 1930’s they were not structurally characterized until many years later.1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9n- (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry.3-6 Notable milestones are the oxidative coupling of Ge94- clusters to oligomers and infinite chains,7-19 their metallation,14-16,20-25 capping by transition-metal organometallic fragments,26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization,35-47 addition of main-group organometallic fragments as exo-bonded substituents,48-50 and functionalization with various organic residues by reactions with organic halides and alkynes.51-58

This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge94- clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2]2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left undisturbed for a few days, the so-layered solutions produced orange crystalline blocks of [K(18-crown-6)]2[Ge9(HCCH2)2]•en which were characterized by single-crystal X-ray diffraction.

The process highlights standard reaction techniques, work-up, and analysis towards functionalized deltahedral Zintl clusters. It is hoped that it will help towards further development and understanding of these compounds in the community at large.

Protocol

1. नाइओबियम ट्यूब की तैयारी नाइओबियम ट्यूबों (नायब) में कटौती से पहले, नायब सफाई समाधान तैयार. एक 500 मिलीलीटर की प्लास्टिक की बोतल में, बाहर उपाय और एक 100 मिलीलीटर सिलेंडर निम्नलिखित स्टॉक समाधान के रू?…

Discussion

यह आंशिक रूप से ऑक्सीकरण नायब ट्यूब को अच्छी तरह से साफ महत्वपूर्ण है. हालांकि, अगर ट्यूब भी लंबे समय नायब सफाई समाधान में छोड़ दिया जाता है, यह गंभीर रूप से ट्यूब की मोटाई के साथ समझौता होगा. इस प्रकार, 10 – …

Disclosures

The authors have nothing to disclose.

Acknowledgements

लेखकों के लिए लगातार वित्तीय सहायता (चे 0,742,365) के लिए और Bruker अपैक्स द्वितीय (चे 0,443,233) diffractometer और Bruker Microtof द्वितीय मास स्पेक्ट्रोमीटर (चे 0,741,793) की खरीद के लिए राष्ट्रीय विज्ञान फाउंडेशन को धन्यवाद देना चाहूंगा. लेखकों को भी CEST सुविधा Micromass जन Quattro नियंत्रण रेखा स्पेक्ट्रोमीटर के अपने प्रयोग के लिए धन्यवाद देना चाहूंगा.

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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Zintl IonsGermaniumFunctionalizationOrganic GroupsRedox ChemistryDeltahedral ClustersReactivityChemistryClusters 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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