我们提出的K高温金属间化合物的前体的合成<sub> 4</sub> GE<sub> 9</sub>,他们在解散乙二胺形成GE<sub> 9</sub<sup> 4 -</sup> deltahedral Zintl离子,炔集群的反应形成有机Zintl离子。后者的特点是通过电质谱解决方案,并通过单晶X-射线衍射固态。
虽然1890年代末和1930年初的Zintl离子之间的日期最初的研究,他们并没有结构上的特点,直到多年以后。1,2它们的氧化还原化学是更年轻的,只是10岁,但尽管这短暂的历史这些离子deltahedral的集群北京时间9 N-(C =硅,锗,锡,铅,N = 2,3,4)。3-6已经显示出有趣的和多样化的反应,并已在迅速发展和令人振奋的新化学前沿的著名的里程碑9月 4锗的氧化耦合–低聚物和无限链,7-19金属化,14-16,20-25集群过渡金属有机碎片,26-34过渡金属原子插入在中心封顶有时被封盖和齐聚,除了主族有机金属碎片外保税取代35-47结合的产业集群,48-50和官能与各种有机残留物与有机卤化物和炔烃的反应。51-58
这后者的有机碎片直接连接集群的发展开辟了一个新的领域,即的有机Zintl化学,为进一步合成的探索,可能是肥沃的,它是一步一步由锗乙烯基合成过程此处描述的集群。最初的步骤概述合成革9 K的4间易制毒化学从戈9 4 –簇后在溶液中提取。这涉及到熔石英玻璃吹,铌容器弧焊,高度空气敏感材料的处理,在手套箱。空气敏感K戈9,然后在框中乙二胺溶解,然后跟我反应3 SiC≡CSiMe的alkenylated。反应,其次是电trospray质谱,而最终的解决方案是用获得单晶包含官能集群[H 2 C = CH戈9-CH = CH 2] 2 – 。用于此目的的解决方案是离心,过滤,并仔细分层与18 – 冠-6的甲苯溶液。离开几天原状,这样层次的解决方案产生的橙色[K(18 -冠-6)] 2 [葛9(HCCH 2)2]•EN由单晶X-射线衍射特征结晶块。
过程中突出反应技术标准,工作,和对官能deltahedral Zintl集群分析。它希望,这将有助于对这些化合物在大进一步发展和社会的理解。
这是重要的清洁以及部分氧化铌管。然而,如果留在管铌清洗液的时间过长,将严重危及管的厚度。因此,10 – 15秒,是势在必行,管,应该是在结束(图3)非常有光泽。后密封石英外套管内,他们应与铌稀溶液清洗了一遍。这将导致轻度欢腾,清洁氧化铌管焊接或玻璃吹制过程中发生的任何地区。但是,要小心不要离开太久溶液蚀刻玻璃(图7B)。
重要的是要确保碱金属?…
The authors have nothing to disclose.
笔者想感谢的持续财政支持(译文-0742365)和国家科学基金会在Bruker APEX II衍射仪(译文-0443233),并在Bruker Microtof-II质谱仪(译文-0741793)购买。笔者也想感谢他们使用的微团的Quattro-LC质谱仪欧夏令时设施。
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% |