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Biology

유기 그룹과 아홉살 원자 Deltahedral Zintl 게르마늄의 이온과 작용화의 합성

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

Summary

우리는 K 중간 엽 성의 전구 물질의 고온 합성을 제시<sub> 4</sub> GE<sub> 9</sub>, 에틸렌 그들의 해산은 GE를 형성하는<sub> 9</sub<sup> 4 -</sup> deltahedral Zintl 이온 및 organo-Zintl 이온을 형성 alkynes와 클러스터의 반응. 후자는 솔루션에 전기 분무 질량 분광법 의해 고체 상태의 단일 크리스탈 X 선 회절에 의해 특성화된다.

Abstract

후반 1890 년대 초반 1930 년대의 사이 Zintl 이온 날짜의 첫 번째 연구는 그들이 구조적으로 몇 년 후까지 특성화되지 않았습니다지만. 1,2 그들의 산화 환원 화학 단지 약 10 년 나이도 젊은이지만,이 짧은 역사에도 불구하고 이러한 deltahedral 클러스터 이온 E 9 N-(E = 씨, GE, SN, PB, N = 2, 3, 4). 이미 흥미롭고 다양한 반응을 보였습니다 빠르게 개발하고 새롭고 흥미로운 화학의 선두 있었 3-6 주목할 이정표가 GE 9 4의 산화 커플링 – 천이 금속 organometallic 조각의 중앙에 전이 금속 원자의 26-34 삽입하여 상한 oligomers과 무한 체인, 7-19들의 metallation, 14-16,20-25에 클러스터 때로 상한 및 oligomerization, 엑소 – 보세 substituents 같은 메인 그룹 organometallic 조각 35-47뿐만 아니라 결합되는 클러스터,유기 halides과 alkynes와 반응하여 다양한 유기 잔류물과 48-50과 작용화. 51-58

클러스터에 직접 유기 조각을 붙이는이 후자의 개발은 더욱 합성 탐험에 대한 잠재적 비옥 새로운 분야, 즉 organo-Zintl 화학을 열었으며, 그것은 게르마늄 – 디비닐의 합성을위한 단계별 절차입니다 클러스터는 본 설명했다. 초기 단계는 K 4의 금속 전구체 GE 9 합성을 설명하는에서 GE 9 4 – 클러스터는 나중 용액의 압축이 풀립니다. 이것은 불고 니오브 컨테이너의 아크 – 용접 및 글러브 박스에서 높은 공기에 민감한 물질로 취급 융합 – 실리카 유리를 포함한다. 공기에 민감한 K 사 GE 9가 다음 상자에 에틸렌에 녹아 후 Me와 반응 3 SIC ≡ CSiMe 3 alkenylated됩니다. 반응은 elec이옵니다trospray 질량 분광법 결과 ​​솔루션은 작용 클러스터 [H 2 C = CH-GE 9-CH = CH 2] 2를 포함하는 하나의 결정을 얻기 위해 사용되는 동안 -. 이를 위해 솔루션은 centrifuged 여과, 그리고 조심스럽게 18 왕관-6의 톨루엔 용액과 함께 상상을 뛰어넘는 세월을 거슬러 올라가있다. 며칠 동안 방해받지 왼쪽, 소위 계층 솔루션의 오렌지색의 결정 블록 [K (18 – 크라운 -6)] 2 [GE 9 (HCCH 2) 2]을 제작 • 실내 단일 크리스탈 X 선 회절 특징으로했다하는 .

프로세스는 표준 반응 기법, 동작 업 및 작용 deltahedral Zintl 클러스터에 대한 분석을 강조 표시합니다. 그것은 그것이 대규모의 사회에서 이러한 화합물의 발전과 이해 향해 도움이 될 것으로 기대된다.

Protocol

1. 니오브 튜브를 준비 니오브 (NB) 튜브를 절단하기 전에, NB-클리닝 솔루션을 준비합니다. 500 ML의 플라스틱 병에서 밖으로 측정하고받은대로 실린더 다음 주식 솔루션을 측정하는 100 ML을 통해 추가할 수 : 110 ML H 2 SO 4를 40 ML HF 이어, 50 ML HNO 3 따라갔다. 잘 섞어서 사용하기 전에 실내 온도에 도달하실 수 있습니다. NB 튜브, 길이 4.5 cm, 그리고 파이프 커터로 ?…

Discussion

그것은 잘 일부 산화 NB 튜브를 세척하는 것이 중요합니다. 튜브가 NB 클리닝 용액에 오래 남아있는 경우 그러나, 이것은 심각하게 튜브의 두께를 손상됩니다. 따라서, 10, '- 15 초 필수적이며, 튜브 끝 (그림 3)에서 매우 전문 있어야합니다. 튜브가 융합된 실리카 자켓 내부에 봉인 후 그들은 묽은 NB의 산성 용액으로 다시 세척해야합니다. 이것은 용접이나 유리 부는 동안 발생 NB 튜브에있는 산화 …

Disclosures

The authors have nothing to disclose.

Acknowledgements

저자들은 지속적인 재정 지원 (CHE-0742365)와 Bruker 에이펙스 II diffractometer (CHE-0443233)와 Bruker Microtof-II 질량 분석계 (CHE-0741793)의 구입을위한 국립 과학 재단 (National Science Foundation)을 감사드립니다. 저자는 또한 Micromass 쿼트로-LC 질량 분석기의 사용을 위해 중부 유럽 표준시 시설을 감사드립니다.

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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