JoVE Journal > Biology
Summary
Abstract
Protocol
Discussion
Disclosures
Acknowledgements
Materials
References
자동 번역
생물학

Syntese av Nine-atom Deltahedral Zintl Ioner av germanium og deres funksjonalisering med organiske grupper

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

Summary

Vi presenterer den høye temperaturen syntese av intermetalliske forløpere K<sub> 4</sub> Ge<sub> 9</sub> Til sin oppløsning i etylendiamintartrat danne Ge<sub> 9</sub<sup> 4 -</sup> Deltahedral Zintl ioner, og reaksjonen av klyngene med alkyner å danne organo-Zintl ioner. Sistnevnte er preget av electrospray massespektrometri i løsninger og ved single-krystall røntgendiffraksjon i solid state.

Abstract

Selv om de første studiene av Zintl ioner dato mellom slutten av 1890 tallet og tidlig 1930-tallet ble de ikke strukturelt preget før mange år senere. 1,2 Deres redoks kjemi er enda yngre, bare omtrent ti år gammel, men til tross for denne korte historien disse deltahedral klynger ioner E 9 n-(E = Si, Ge, Sn, Pb, n = 2, 3, 4). har allerede vist interessant og mangfoldig reaktivitet og har vært i forkant av rask utvikling og spennende ny kjemi 3-6 Kjente milepæler er oksidativ kopling av Ge 9 4 – klynger til oligomerer og uendelige kjeder, 7-19 deres metallation og 14-16,20-25 capping av overgang-metall metallorganiske fragmenter, 26-34 innsetting av en overgang-metal atom i sentrum av klyngen som er noen ganger kombinert med tildekking og oligomerization, 35-47 tillegg av hoved-gruppe metallorganiske fragmenter som exo-limte substituenter,48-50 og funksjonalisering med ulike organiske rester ved reaksjoner med organiske halogenider og alkyner. 51-58

Denne sistnevnte utviklingen av feste organiske fragmenter direkte til de klynger har åpnet opp et nytt felt, nemlig organo-Zintl kjemi, som er potensielt fruktbar for videre syntetiske utforsking, og det er steg-for-trinn prosedyre for syntese av germanium-divinyl klynger beskrevet. De første trinnene skissere syntesen av en intermetalliske forløperen K 4 Ge 9 hvorfra Ge 9 4 – klynger er hentet senere i løsningen. Dette innebærer smeltet-silika glass blåser, lysbuesveising av niob containere, og håndtering av svært air-sensitivt materiale i en hanskerommet. The air-sensitive K 4 Ge 9 blir deretter oppløst i etylendiamintartrat i boksen og deretter alkenylated ved en reaksjon med meg tre SiC ≡ CSiMe tre. Reaksjonen etterfølges av electrospray massespektrometri mens den resulterende løsningen brukes for å skaffe enkrystaller inneholder functionalized klyngene [H 2 C = CH-Ge 9-CH = CH 2] 2 -. For dette formålet løsningen sentrifugeres, filtrert, og forsiktig lagvis med en toluen løsning av 18-krone-6. Venstre uforstyrret i noen dager, produsert så lag løsninger oransje krystallklare blokker av [K (18-krone-6)] 2 [Ge 9 (HCCH 2) 2] • EN som ble preget av enkelt-krystall røntgendiffraksjon .

Prosessen fremhever standard reaksjon teknikker, virke-up og analyse mot functionalized deltahedral Zintl klynger. Det er å håpe at det vil hjelpe på videre utvikling og forståelse av disse forbindelsene i samfunnet for øvrig.

Protocol

1. Forbereder niob Tubes Før kutte niob (Nb) rør, forberede Nb-rengjøringsmiddel. I en 500 ml plastflaske, måle ut og legg via en 100 ml målesylinder følgende stamløsninger som mottatt: 110 ml H 2 SO 4, etterfulgt av 50 ml HNO 3, etterfulgt av 40 ml HF. Bland godt og la nå romtemperatur før bruk. Mål Nb tube, 4,5 cm i lengde, og kuttet med en rørkutter. Unngå knekk på slangen. Gjenta 3 ganger. I et godt ventilert røyk-hette, plasserer de fire …

Discussion

Det er viktig å rengjøre godt delvis oksidert NB rør. Men hvis rørene er igjen for lenge i Nb renhold løsning, vil dette sterkt redusere tykkelsen på røret. Dermed 10 – 15 sekunder er avgjørende, og rørene skal være veldig skinnende på slutten (Fig. 3). Etter at rørene er forseglet inne i smeltet silisiumdioksid jakke, bør de rengjøres igjen med en fortynnet Nb syre løsning. Dette bør resultere i mild livslysten, rengjøring eventuelle oksidert områder på NB rør som skjedde under sveising eller glass-…

Disclosures

The authors have nothing to disclose.

Acknowledgements

Forfatterne ønsker å takke National Science Foundation for kontinuerlig økonomisk støtte (CHE-0742365) og for kjøp av en Bruker APEX II Diffractometer (CHE-0443233) og en Bruker Microtof-II massespektrometer (CHE-0741793). Forfatterne vil også gjerne takke CEST anlegget for deres bruk av 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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Tags

Zintl IonsGermaniumFunctionalizationOrganic GroupsRedox ChemistryDeltahedral ClustersReactivity화학Clusters 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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