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Biologie

Synthese van Nine-atoom Deltahedral Zintl ionen van germanium en hun functionalisering met organische groepen

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

Summary

We presenteren de hoge temperatuur synthese van intermetallische voorlopers K<sub> 4</sub> Ge<sub> 9</sub> Hun oplossing in ethyleendiamine vormen Ge<sub> 9</sub<sup> 4 -</sup> Deltahedral Zintl ionen, en de reactie van de clusters met alkynen tot organo-Zintl ionen vormen. Deze worden gekenmerkt door electrospray massaspectrometrie in oplossingen en eenkristal röntgendiffractie in de vaste toestand.

Abstract

Hoewel de eerste studies van Zintl ionen datum tussen de late jaren 1890 en vroege jaren 1930 werden ze niet structureel gekarakteriseerd pas vele jaren later. 1,2 Hun redox chemie is nog jonger, ongeveer tien jaar oud, maar ondanks deze korte geschiedenis van deze deltahedral clusters ionen E 9 n-(E = Si, Ge, Sn, Pb, n = 2, 3, 4). hebben al aangetoond interessante en diverse reactiviteit en zijn in de voorhoede van zich snel ontwikkelende en spannende nieuwe chemie 3-6 Opmerkelijke mijlpalen zijn de oxydatieve Ge 9 4 – clusters oligomeren en oneindige ketens, 7-19 hun metallering, 14-16,20-25 plafond door overgangsmetaal-organometallische fragmenten 26 tot 34 inbrengen van een overgangsmetaal-atoom in het midden van het cluster die soms wordt gecombineerd met aftopping en oligomerisatie, 35-47 toevoeging van de belangrijkste-groep organische fragmenten als exo-gebonden substituenten,48-50 en functionalisering met diverse organische reststoffen door reacties met organische halogeniden en alkynen. 51-58

Deze laatste ontwikkeling van het bevestigen van organische fragmenten rechtstreeks naar de clusters opent een nieuw veld, namelijk organische Zintl chemie, die potentieel vruchtbaar voor verdere synthetische verkenningen, en het is de stap-voor-stap procedure voor de synthese van germanium-divinyl clusters die hierin worden beschreven. De eerste stappen beschrijven de synthese van een precursor van intermetallische K 4 Ge 9, waaruit het Ge 9 4 – clusters later in oplossing geëxtraheerd. Dit houdt in fused-silica glas blazen, booglassen, van niobium containers, en het hanteren van zeer lucht-gevoelige materialen in een handschoenenkastje. De luchtgevoelig K 4 Ge 9 wordt opgelost in ethyleendiamine in het vak en alkenylated door reactie met Me 3 SiC ≡ CSiMe 3. De reactie werd gevolgd door electrospray massaspectrometrie terwijl de verkregen oplossing wordt gebruikt voor het verkrijgen enkele kristallen die de gefunctionaliseerde clusters [H 2 C = CH-Ge 9-CH = CH-2] 2 -. Hiertoe wordt de oplossing gecentrifugeerd, gefiltreerd en zorgvuldig lagen met een tolueenoplossing van 18-kroon-6. Ongestoord dat slechts enkele dagen, de zogenaamde gelaagde oplossingen verkregen oranje kristallijn blokken [K (18-kroon-6)] 2 [Ge 9 (HCCH 2) 2] • en die gekenmerkt door eenkristal röntgendiffractie .

Het proces benadrukt standaard reactie technieken, werk-up, en de analyse naar gefunctionaliseerde deltahedral Zintl clusters. Het is te hopen dat het zal helpen naar een verdere ontwikkeling en het begrip van deze verbindingen in de samenleving in het algemeen.

Protocol

1. Voorbereiden Niobium Tubes Voor het snijden van de niobium (Nb) buizen, voor te bereiden Nb-reinigingsoplossing. In een 500 ml plastic fles afmeten en voeg via een maatcilinder van 100 ml volgende voorraadoplossingen zoals ontvangen: 110 ml H 2 SO 4, gevolgd door 50 ml HNO3, gevolgd door 40 ml HF. Meng goed en laat het bereiken van kamertemperatuur voor gebruik. Meet de Nb buis, 4,5 cm in lengte, en snijd met een pijpsnijder. Vermijd het knikken van de slang. Herh…

Discussion

Het is belangrijk om goed te reinigen de gedeeltelijk geoxideerde Nb buizen. Indien de buizen te lang in de Nb reinigingsoplossing, dit ernstig gevaar de dikte van de buis. Zo, 10 – 15 seconden zijn noodzakelijk en de buizen moeten zeer glanzend te zijn aan het einde (afb. 3). Nadat de buizen worden afgedicht in de gesmolten silica mantel moeten weer worden gereinigd met een verdunde zuuroplossing Nb. Dit moet resulteren in een lichte pareling, het reinigen van een geoxideerde gebieden op Nb buizen die zich hebben voorg…

Divulgations

The authors have nothing to disclose.

Acknowledgements

De auteurs willen graag de National Science Foundation bedanken voor de voortdurende financiële steun (CHE-0742365) en voor de aankoop van een Bruker APEX II diffractometer (CHE-0443233) en een Bruker Microtof-II massaspectrometer (CHE-0741793). De auteurs willen ook graag CEST faciliteit bedanken voor hun gebruik van de Micromass Quattro-LC-massaspectrometer.

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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