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Abstract
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Biologie

Syntese af Ni-atom Deltahedral Zintl Ioner af germanium og deres Funktionalisering med organiske grupper

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

Summary

Vi præsenterer høj temperatur syntese af intermetalliske precursorer K<sub> 4</sub> Ge<sub> 9</sub>, Til deres opløsning i ethylendiamin danne Ge<sub> 9</sub<sup> 4 -</sup> Deltahedral Zintl ioner, og reaktionen af ​​klynger med alkyner til dannelse organiske Zintl ioner. Sidstnævnte er karakteriseret ved elektrospray massespektrometri i opløsninger og enkelt-krystal røntgendiffraktion i fast tilstand.

Abstract

Selv om de første undersøgelser af Zintl ioner dato mellem slutningen af 1890 og begyndelsen af 1930 har de ikke strukturelt præget først mange år senere. 1,2 Deres redox kemi er endnu yngre, kun omkring ti år gammel, men trods denne korte historie disse deltahedral klynger ioner E 9 n-(E = Si, Ge, Sn, Pb, n = 2, 3, 4). har allerede vist, interessant og varieret reaktivitet og har været på forkant med hastig udvikling, og nye spændende kemi 3-6 bemærkelsesværdige milepæle er den oxidative kobling af Ge 9 4 – klynger til oligomerer og uendelig kæder, 7-19 deres metallering, 14-16,20-25 capping af overgangsmetalioner organometalliske fragmenter, 26-34 insertion af et overgangsmetal atom i midten af klyngen som undertiden kombineret med loft og oligomerisering, 35-47 tilsætning af hoved-gruppe metalorganiske fragmenter som exo-bonding substituenter,48-50 og funktionalisering med forskellige organiske rester ved reaktion med organiske halogenider og alkyner. 51-58

Sidstnævnte udvikling af vedhæfte organiske fragmenter direkte til de klynger har åbnet op for et nyt felt, nemlig organiske Zintl kemi, som er potentielt frugtbar for yderligere syntetiske sonderinger, og det er trin-for-trin procedure for syntesen af ​​germanium-divinyl klynger beskrevet heri. De indledende trin skitserer syntesen af en intermetallisk prækursor for K 4 Ge 9, hvorfra Ge 9 4 – klynger ekstraheres senere i opløsning. Dette indebærer kvartsglas glasblæsning, lysbuesvejsning af niobium beholdere, og håndtering af meget luft-følsomme materialer i en handskekasse. Luft-følsomme K 4 Ge 9 opløses derefter i ethylendiamin i boksen og derefter alkenylated ved en reaktion med Me3 SiC ≡ CSiMe 3. Reaktionen følges ved elektrotrospray massespektrometri mens den resulterende opløsning anvendes til opnåelse af enkelte krystaller indeholdende funktionaliserede grupper [H2C = CH-Ge 9-CH = CH2] 2 -. Til dette formål opløsningen centrifugeres, filtreres og forsigtigt lagt med en toluenopløsning af 18-krone-6. Efterlades uforstyrret i nogle få dage, så-lagdelte opløsninger fremstillet orange krystallinsk blokke af [K (18-krone-6)] 2 [Ge 9 (Haagerkonferencens 2) 2] • en, der blev karakteriseret ved en enkelt-krystal røntgendiffraktion .

Processen sætter fokus på standard-reaktion teknikker, oparbejdning og analyse i retning af funktionaliserede deltahedral Zintl klynger. Det er håbet, at det vil medvirke til yderligere udvikling og forståelse af disse forbindelser i samfundet som helhed.

Protocol

1. Forberedelse Niobium Rør Før du klipper de niobium (Nb) rør, forberede Nb-rengøringsmiddel. I en 500 ml plastflaske, ud måle og tilsættes via en 100 ml målecylinder følgende stamopløsninger som modtaget: 110 ml H2 SO4, efterfulgt af 50 ml HNO3, efterfulgt af 40 ml HF. Bland godt og lad nå stuetemperatur før brug. Måle Nb røret, 4,5 cm i længde, og snit med en rørskærer. Undgå kinkning slangen. Gentag 3 gange mere. I et godt ventileret røg-hætte, …

Discussion

Det er vigtigt at rengøre og de delvist oxiderede Nb rør. Hvis rørene efterlades for længe i Nb renseopløsningen vil dette alvorligt forringe tykkelsen af ​​røret. Således, 10 – 15 sekunder er nødvendigt, og rørene skal være meget skinnende ved enden (fig. 3). Efter at rørene er forseglet inde i kvartsglas kappen skal de renses igen med en fortyndet Nb syreopløsning. Dette bør resultere i mild luftudvikling, rengøring eventuelle oxiderede områder på Nb rør, der opstod under svejsning eller glaspuste…

Divulgations

The authors have nothing to disclose.

Acknowledgements

Forfatterne vil gerne takke National Science Foundation til kontinuerlig økonomisk støtte (CHE-0.742.365) og til køb af en Bruker APEX II diffraktometer (CHE-0.443.233) og en Bruker Microtof-II massespektrometer (CHE-0.741.793). Forfatterne vil også gerne takke CEST facilitet for deres brug af Micromass Quattro-LC massespektrometer.

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 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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