Name: 1,3,5-triphenylbenzene and corannulene as electron receptors for lithium solvated electron solutions
Uploaded: 2016-10-10T13:00:00.000+00:00
Duration: 6 min 56 s
Description: Watch this Scientific Journal Video about 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions at JoVE.com

作者为这个项目确认来自新加坡教育部2级研究基金（项目MOE2013-T2-2-002）资金。

1.准备程序1,3,5-三苯（1） <ol><li>放置苯乙酮的100ml无水乙醇的混合物（4.0克，33.3毫摩尔）和到装有磁力搅拌器，回流冷凝器，氮气进口，鼓泡器，滴液漏斗和温度计的圆底三颈250ml烧瓶中。使用滴液漏斗，在0℃在一个部分的四氯化硅（11.9克，8.0毫升，70.2毫摩尔，2.1当量）添加到该混合物在氮气下。 </li><li>观察的氯化氢气体的演变为10分钟。然后搅拌，在40℃20小时，将反应混合物。 </li><li>冷却反应混合物至23℃，并于200克的水与冰混合，倾（1:1质量比）。 </li><li>用二氯甲烷萃取（2×100毫升）使用提取漏斗所得混合物。 </li><li>用饱和NaCl溶液（100毫升），干燥超过15克无水硫酸镁的洗合并的萃取一次。过滤液体部分关闭，然后我们集中ING旋转蒸发器。 </li><li>通过重结晶从乙醇中纯化产物（溶解于乙醇，随后通过溶剂的部分蒸发最小量，在6℃下保持过夜，并快速过滤），得到2.2克（收率63％）1,3,5-三苯基苯的（1），为浅黄色晶体。 注:1 H-NMR（400兆赫，CDCL 3）:δ= 7.41（M，3H），7.50（M，6H），7.72（D，6H，J = 7.33Hz），7.80（S，3H）13 C-NMR（400兆赫，CDCL 3）:δ= 125.21，127.39，127.57，128.88，141.18，142.38。 </li></ol> 2. LiSES准备与1,3,5-三苯<ol><li>的1,3,5-三苯基苯基LiSES制备 注:本文中使用1,3,5-三苯合成按上述程序。 1,3,5-三苯基于LiSES由李均用x表示TPB（THF）24.7，其中x代表李:PAH摩尔比和TPB表示1,3,5-三苯。李准备点¯xTPB（THF）24.7在通过以下步骤常温充满氩气的手套箱内: <ol><li>量出金属锂，THF和TPB的明确定义的数量分别手套箱内实现Li的目标摩尔组分x TPB（THF）24.7对于x = 1，2，3和4使用41.6毫克，83.3毫克，124.9毫克，166.6毫克李的对于x = 1，2，3和4分别。 </li><li>对于四个LiSES样品被制备，溶解1.84克TPB的12毫升THF的内部四个独立的玻璃瓶表格12毫升每瓶TPB（THF）中24.7的无色溶液。在所有的解决方案，使用0.5M的1,3,5-三苯。 </li><li>加权金属箔丽添加到四瓶和密封用封口膜的瓶子。 </li><li>搅拌在使用玻璃包被的磁性搅拌器以确保金属Li的完全溶解每瓶混合物过夜。 </li></ol></li><li>电导率测量<ol><li>携带所有电导率测量使用基于四电极技术标准电导池探针。小区探头连接到一米。探针具有二级函数来测量溶液的温度在同一时间和同时显示电导率和温度的测量。 </li><li>在此之前的测量，校准用50毫升标准0.01米氯化钾水溶液的电导率探头的手套箱以外的制造商提供的电表。 </li><li>执行所有用于基于1,3,5-三苯基苯LiSES的电导率测量， 为 Li x TPB（THF）24.7对于x = 1，2，3，4的手套箱内。 </li><li>对于这些LiSES中，倾出样品放入一个短玻璃筒和将电极浸入溶液中。记录电导率测量在一段一到两个小时，直到每个样品返回到环境温度。返回到环境温度取每个样品的时间为〜1-2小时。探头W¯¯病保持浸渍样品为电导率测量的整个持续时间英寸</li></ol></li></ol> 3.碗烯<ol><li>基于碗烯-LiSES的制备 注:本文所用的碗烯是使用多级文献程序在物理学院和数学科学学院，南洋理工大学合成9基于碗烯-LiSES被李用x表示心病（THF）247，其中x代表李:PAH摩尔比林表示碗烯。制备的 Li x心病（THF）247在环境温度下通过以下步骤充满氩气的手套箱内: <ol><li>量出金属锂，THF和肺心病的明确定义的数量分别手套箱内达到目标摩尔组成的 Li x心病（THF）247对于x = 1，2，3，4和5，使用4.2毫克，8.3毫克， 12.5毫克，16.6毫克和对于x = 1，2，3，分别为4和5 20.8毫克李。 </li><li> NEXT，对每个五个LiSES样品（X = 1，2，3，4和5）制备，溶解0.15克肺心病的在里面五个独立玻璃瓶12毫升THF中以形成12毫升心病的无色溶液（THF）247在每个瓶子。使用0.05米的碗烯浓度）。 </li><li>接下来，添加称重金属箔李来林（THF）247的五瓶和密封用封口膜的瓶子。 </li><li>搅拌在使用玻璃包被的磁性搅拌器以确保金属锂完全溶解每瓶混合物过夜。 </li></ol></li><li>电导率测量<ol><li>电导率与温度的测量，除去各含有的 Li x心病（THF）247对于x = 1，2，3，4和5分别从手套箱五瓶，用对薄膜的附加层包起来，并浸入其内部填充有干冰的绝缘泡沫塑料容器。 注:LiSES样品没有接触到续与任一湿气或氧气作用而手套箱外，因为将瓶子密封。 </li><li>通过保持每个瓶子浸没在干冰约30分钟被转移回手套箱电导率测量之前冷却每瓶下降到约10℃。 </li><li>吹扫手套箱至少5次，每次冷却的样品，以确保没有缩合痕量的水伴随瓶子放回手套箱的前厅。 </li><li>在其中导电率随温度的测量，收集用于基于萘LiSES试样1的方式，测量锂的电导率相似点¯x心病（THF）247（X = 1，2，3，4，5），历时一至两个小时，才被每个样品返回到环境温度。探针将保持浸渍的样品电导率测量的整个持续时间英寸</li></ol></li></ol>

<ol>
	<li>Tan, K. S., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Physical-Chemical+and+Electrochemical+Studies+of+the+Lithium+Naphthalenide+Anolyte.">Physical-Chemical and Electrochemical Studies of the Lithium Naphthalenide Anolyte.</a> Electrochim Acta. 180, 629-635 (2015).</li><li>Tan, K. S., Grimsdale, A. C., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+Characterisation+of+Biphenyl-Based+Lithium+Solvated+Electrons+Solutions.">Synthesis and Characterisation of Biphenyl-Based Lithium Solvated Electrons Solutions.</a> J Phys Chem B. 116, 9056-9060 (2012).</li><li>Rinaldi, A., Tan, K. S., Wijaya, O., Wang, Y., Yazami, R., Menictas, C., Skyllas-Kazacos, M., Lim, T. M., Hughes, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ch.+11.">Ch. 11.</a> Advances in batteries for large- and medium-scale energy storage applications in power systems and electric vehicles. , (2014).</li><li>Wang, Y., Tan, K. S., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Materials Challenges In Alternative &amp; Renewable Energy (MCARE 2014). , (2014).</li><li>Yazami, R., Tan, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> in 8th annual Li Battery Power. , (2012).</li><li>Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hybrid+Electrochemical+Generator+With+A+Soluble+Anode.">Hybrid Electrochemical Generator With A Soluble Anode.</a> US patent. , (2010).</li><li>Yazami, R., Tan, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Liquid+Metal+Battery.">Liquid Metal Battery.</a> US patent. , (2015).</li><li>Lim, Z. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+assessment+of+new+cyclopenta-2,4-dienone+derivatives+for+energy+storage+applications.">Synthesis and assessment of new cyclopenta-2,4-dienone derivatives for energy storage applications.</a> Synthetic Met. 200, 85-90 (2015).</li><li>Butterfield, A. M., Gilomen, B., Siegel, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kilogram-Scale+Production+of+Corannulene.">Kilogram-Scale Production of Corannulene.</a> Org. Process Res. Dev. 16, 664-676 (2012).</li><li>Elmorsy, S. S., Pelter, A., Smith, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+direct+production+of+tri-+and+hexa-substituted+benzenes+from+ketones+under+mild+conditions.">The direct production of tri- and hexa-substituted benzenes from ketones under mild conditions.</a> Tetrahedron Lett. 32, 4175-4176 (1991).</li><li>Zabula, A. V., Filatov, A. S., Spisak, S. N., Rogachev, A. Y., Petrukhina, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Main+Group+Metal+Sandwich:+Five+Lithium+Cations+Jammed+Between+Two+Corannulene+Tetraanion+Decks.">A Main Group Metal Sandwich: Five Lithium Cations Jammed Between Two Corannulene Tetraanion Decks.</a> Science. 333, 1008-1011 (2011).</li></ol>

作者什么都没有透露。

对于基于1,3,5-三苯基苯LiSES，具有光色的样品表明，它具有溶剂化电子的低浓度。 的 Li x TPB（THF）24.7（对于x = 1，2，3，4）展示在其导电率与X A行为类似于看到从联苯和萘1制成LiSES，2。还有在传导性的初始增加与李增加:PAH比为1〜2和导电性在进一步增加的摩尔比为3，4，用李4 TPB（THF）24.7的电导率值比对Li 1 TPB（THF）24.7<...

锂溶剂化电子溶液（LiSES）使用简单的两环多环芳烃（PAH）例如联苯和萘可以潜在地用作在充燃料锂电池1-7液态阳极制备。在LiSES，这些简单的PAH分子担任电子受体从溶解金属锂溶剂化电子。 来自这两个环系统进展，作者自然后进行电导率测量研究其上使用更复杂的多环芳烃制备，与基环戊-2,4-二烯酮衍生物8的起始LiSES。这些多环芳烃包括更大的多环芳烃（&gt;两个苯环），并纳入其芳香环的取代基的多环芳烃。有两个以上的环A大的PAH分子预计容纳每多环芳烃分子更锂原子比任联苯或萘从而导致具有更高的能量密度LiSES。 introduc的目标ING取代成多环芳烃是使PAH更易于接受电子而变得更加稳定在LiSES聚阴离子。 作为不断努力开发具有更高的能量密度LiSES的一部分，本文将通过文献方法9以及1,3,5-三苯做碗烯制备LiSES的特征报告，由城规会略加修改文献10合成。 1,3,5-三苯基苯， 如图1（1），可以被分类为与在位置3两个附加苯基环和相同的环的5联苯衍生物。因为该分子具有4个苯环，应该摄取每分子李，这比对联苯更多的4个原子（每PAH锂的最大2.5摩尔当量在0.5M溶液）和萘（&lt;每分子锂的2.5摩尔当量） 。 碗烯是五环的PAH布置成碗形， 如图1（2）。 Zabula 等人 11表明金属锂溶解于碗烯/四氢呋喃（THF）中的溶液，以形成具有夹在碗烯的两个稳定tetraanions之间的五个Li +离子的溶液的可行性。 <img alt="图1" src="/files/ftp_upload/54366/54366fig1.jpg" /> 图1:1,3,5-三苯基苯的分子结构（1）和碗烯（2）1,3,5-三苯基苯是在相同的环的位置3和5划分为联苯衍生物具有两个附加苯基环。 。碗烯是一种五环PAH与布置成碗状的五个苯环。 <a href="https://www.jove.com/files/ftp_upload/54366/54366fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 因此，无论1,3,5-三苯和碗烯是高能量的潜在候选人密度LiSES。

<table><tbody><tr><td>Tetrahydrofuran Anhydrous, &amp;#8805;99.9%, Inhibitor-free</td><td>Sigma Aldrich</td><td>401757-100ML</td><td></td></tr><tr><td>Lithium Foil&amp;nbsp;</td><td>Alfa Aesar</td><td>010769.14</td><td></td></tr><tr><td>Cond 3310 Conductivity Meter</td><td>WTW</td><td>Not Applicable</td><td></td></tr><tr><td>1,3,5-triphenylbenzene</td><td></td><td></td><td>Synthesized from acetophenone according to procedure described in literature</td></tr><tr><td>Silicon tetrachloride</td><td>Sigma Aldrich</td><td>215120-100G</td><td></td></tr><tr><td>acetophenone</td><td>TCI</td><td>A0061-500g</td><td></td></tr><tr><td>Ethanol</td><td>Merck Millipore</td><td>1.00983.2511</td><td></td></tr><tr><td>Corannulene</td><td></td><td></td><td>Synthesized by literature procedure</td></tr></tbody></table>

1,3,5-triphenylbenzene and corannulene as electron receptors for lithium solvated electron solutions

作者对锂溶剂化电子解决方案（LiSES）进行传导的研究报告使用两种类型的多环芳烃（PAH），即1,3,5-三苯和碗烯，作为电子受体的准备。固体多环芳烃首先溶解在四氢呋喃（THF）以形成溶液。然后金属锂溶解于这些PAH / THF溶液，得到蓝色或蓝绿色的解决方案，颜色的指示溶剂化电子的存在。在上1,3,5-三苯基苯基LiSES进行环境温度，由李表示电导率的测量点¯xTPB（THF）24.7（X = 1，2，3，4），表现出与锂的增加电导率的增加: PAH比从X = 1〜2但是，导电性逐渐在进一步增加的比率减小。确立的导电点¯xTPB（THF）24.7对于x = 4比对于x更低</eM&gt; = 1，这样的行为是相似的，从联苯和萘制备的以前报道LiSES的。电导率与基于碗烯-LiSES温度测量，由李用x表示心病（THF）247（X = 1，2，3，4，5），显示出与负斜率的线性关系，表明类似金属的行为，以联苯和萘基于LiSES。

不同量的锂和1,3,5-三苯基苯用THF的混合物之间的反应给出蓝绿色或深蓝色溶液， 如图2的光色表示LiSES的特定样品具有溶剂化电子的低浓度。 1,3,5-三苯基苯演示用的锂增加电导率的增加:在0.5M THF溶液（ 见表1）的PAH比为1〜2。然而，电导率值逐渐在进一步增加的摩尔比减小。李电导率值:PAH = 4比李甚至更低:PAH = 1，此行为是类似于看到从联苯和萘1，2发LiSES。 <table...

Watch this Scientific Journal Video about 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions at JoVE.com

1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using 1,3,5-triphenylbenzene (TPB) and corannulene as electron receptors.

1,3,5-三苯和碗烯作为电子受体锂溶剂化电子解决方案

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using two types of polyaromatic ...

135-triphenylbenzene-corannulene-as-electron-receptors-for-lithium

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Reactions of Aromatic Compounds

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7.7K 次观看.  Nanyang Technological University. The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using 1,3,5-triphenylbenzene (TPB) and corannulene as electron receptors.

视频: 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g.&#160;changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g.&#160;on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li-ion and Na-ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of devices

正极材料的同步辐射技术锂离子和钠离子电池表征

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

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工程学

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

1,6-酮酯高立体选择性合成离子液体介导:三组分反应启用快速进入低分子量胶凝剂的新型类

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

化学

Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

The main purpose of this video is to show 6 reaction steps of a convergent synthesis and prepare a complex molecule containing up to three nonplanar polyaromatic units, which are two corannulene moieties and a racemic hexahelicene linking them. The compound described in this work is a good host for fullerenes. Several common organic reactions, such as free-radical reactions, C-C coupling or click chemistry, are employed demonstrating the versatility of functionalization that this compound can accept. All of these reactions work for planar aromatic molecules. With subtle modifications, it is possible to achieve similar results for nonplanar polyaromatic compounds.

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

Here, we present a protocol to synthesize a complex organic compound comprised of three nonplanar polyaromatic units, assembled easily with reasonable yields.

一个碗烯官能Hexahelicene的铜（Ⅰ）制备催化的非平面多环芳烃单位炔叠氮化物环加成

The main purpose of this video is to show 6 reaction steps of a convergent synthesis and prepare a complex molecule containing up to three nonplanar ...

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents warrants proper technique, thorough training, and proper personal protective equipment. To aid in the training of researchers using organolithium reagents, a thorough, step-by-step protocol for the safe and effective use of tert-butyllithium on an inert gas line or within a glovebox is described. As a model reaction, preparation of lithium tert-butyl amide by the reaction of tert-butyl amine with one equivalent of tert-butyl lithium is presented.

The safe and proper use of organolithium reagents is described.

使用有机锂试剂的一个协议安全的锂化反应

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

钯<em&gt;ñ</em&gt; - 杂环碳烯配合物:苯并咪唑盐的合成和碳 - 碳键合反应中的催化活性

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

A reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented, based on modifications of existing protocols that derive from initial 2-bromo-2-butene lithiation followed by acid mediated dienol cyclization. The revised synthesis and purification of the ligand avoids the use of mechanical stirring while still permitting access to significant quantities (39 g) of Cp*H in good yield (58%). The procedure offers other additional benefits, including a more controlled quench of excess lithium during the production of the intermediate heptadienols and a simplified isolation of Cp*H of sufficient purity for metallation with transition metals. The ligand was subsequently used to synthesize [Cp*MCl2]2 complexes of both iridium and ruthenium to demonstrate the utility of the Cp*H prepared and purified by our method. The procedure outlined herein affords substantial quantities of a ubiquitous ancillary ligand support used in organometallic chemistry while minimizing the need for specialized laboratory equipment, thus providing a simpler and more accessible entry point into the chemistry of 1,2,3,4,5-pentamethylcyclopentadiene.

Reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented. The revised protocol for the synthesis and purification of the ligand minimizes the need for specialized laboratory equipment while simplifying reaction workups and product purification. Use of Cp*H in the synthesis of [Cp*MCl2]2 complexes (M = Ru, Ir) is also described.

访问有价值的配体为支持过渡金属:1,2,3,4,5-五甲基环戊二烯的一种改进，中级规模制备

A reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented, based on modifications of existing protocols that ...

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

A protocol for the fabrication of electrochemically active LiPON-based solid-state lithium-ion nanobatteries using a focused ion beam is presented.

基于 LiPON 的固态锂离子 Nanobatteries 的聚焦离子束制备方法在原位测试中的研究

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

半导体回转金属硫框架结晶的硫醇构建块的合成

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Protocols for the isolation of the commonly employed cyclic (alkyl)(amino) carbene (CAAC) and N-heterocyclic carbene (NHC) are reported. Furthermore, the synthesis of their mixed CAAC&#8211;NHC &#8220;Wanzlick&#8221; dimer and the synthesis of the related stable organic &#8220;olefin&#8221; radical are presented. The main goal of this manuscript is to give a detailed and general protocol for the synthetic chemist of any skill level on how to prepare free heterocyclic carbenes by deprotonation using filter cannulas. Due to the air-sensitivity of the synthesized compounds, all experiments are performed under inert atmosphere using either Schlenk technique or a dinitrogen filled glovebox. Controlling Wanzlick&#8217;s equilibrium (i.e., the dimerization of free carbenes), is a crucial requirement for the application of free carbenes in coordination chemistry or organic synthesis. Thus, we elaborate on the specific electronic and steric requirements favoring the formation of dimers, heterodimers, or monomers. We will show how proton catalysis allows for the formation of dimers, and how the electronic structure of carbenes and their dimers affects the reactivity with either moisture or air. The structural identity of the reported compounds is discussed based on their NMR spectra.

We present protocols for the isolation of stable heterocyclic carbenes. The synthesis of a cyclic (alkyl)(amino) carbene (CAAC) and an N-heterocyclic carbene (NHC) is demonstrated using filter cannulas and Schlenk technique. We furthermore present the synthesis of the related oxygen-sensitive, electron-rich mixed &#8220;Wanzlick dimer&#8221; and the reduced stable organic radical.

分离游离卡本内斯、其混合二聚体和有机自由基

Protocols for the isolation of the commonly employed cyclic (alkyl)(amino) carbene (CAAC) and N-heterocyclic carbene (NHC) are reported. Furthermore, the ...

氧化还原活性 MOF 固态电化学的磁力表征

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs show outstanding performance in terms of gravimetric or areal capacitance and cyclic stability, unfortunately their electrochemical mechanisms are not well understood in most cases. Traditional spectroscopic techniques, such as X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS), have only provided vague and qualitative information about valence changes of certain elements, and the mechanisms proposed based on such information are often highly disputable. In this article, we report a series of standardized methods, including the fabrication of solid-state electrochemical cells, electrochemistry measurements, the disassembly of cells, the collection of MOF electrochemical intermediates, and physical measurements of the intermediates under the protection of inert gases. By using these methods for quantitatively clarifying the electronic and spin state evolution within a single electrochemical step of redox-active MOFs, one can provide clear insight into the nature of electrochemical energy storage mechanisms not only for MOFs, but also for all other materials with strongly correlated electronic structures.

作者聚焦：氧化还原活性金属有机框架固态电化学中中间体的磁力表征  

Ex situ magnetic surveys can directly provide bulk and local information on a magnetic electrode to reveal its charge storage mechanism step by step. Herein, electron spin resonance (ESR) and magnetic susceptibility are demonstrated to monitor the evaluation of paramagnetic species and their concentration in a redox-active metal-organic framework (MOF).

氧化还原-活性金属-有机骨架固态电化学中中间体的磁力表征

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs ...