Name: accessing valuable ligand supports for transition metals: a modified, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene
Uploaded: 2017-03-20T14:00:00.000+00:00
Duration: 9 min 45 s
Description: Watch this Scientific Journal Video about Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene at JoVE.com

我们感谢美国国家科学基金会（CHE-1300508）和圣玛丽山大学（启动和夏季学院发展）慷慨支持这项工作。本鲁珀特（特拉华大学，质谱设施）被确认为LIFDI质谱分析鉴定。

1的异构体混合物的合成3,4,5-三甲基-2,5- heptadien -4-醇<ol><li> 填充干燥烘箱，500毫升的烧杯中，用200ml己烷中并用烘箱干燥表玻璃覆盖。 <ol><li>在一个空罩，用干净的剪刀剪下锂丝的一半英寸件。擦拭纸巾上的每个锂片以除去过量的矿物油，直至所有油似乎是从金属表面除去，并且在该含烧杯己烷放置。 </li><li>填充干燥烘箱，250毫升烧杯用100ml己烷中并用烘箱干燥表玻璃覆盖。去皮天平上此设置。 </li><li>用烘箱干燥钳，从第一烧杯除去锂丝，在一个干净的纸巾迅速擦拭以除去任何残余的油或己烷，并且转移到配衡烧杯中。直到锂丝14.0克（2.03摩尔）被加入到烧杯中重复这一过程。 </li></ol></li><li> 附加一个烘箱干燥，1升三颈烧瓶装备PED用氩气的通风橱中的流动下搅拌棒到的Schlenk线。加热枪将烧瓶几分钟，并允许它在氩气下冷却。 注意:这是使用氩气，以防止锂和二氮之间的电位反应，以形成氮化锂重要。 <ol><li>一旦冷却，用钳子迅速擦拭纸巾上的锂片，然后将锂转移到该烧瓶中在氩气逆流。 </li><li>淹没在矿物油中的任何过量的锂带进行存储。冲洗钳和剪刀与空水槽大量的水。用纸巾擦干每淹没在水中的毛巾在水槽。 注:无溶剂瓶或纸巾应水槽附近。 <ol><li>浸入已用于切割在水和地点半填充的碗锂在一个空的水槽任何纸巾或手套。在一个空罩，慢慢倒入从1.1-1.1.3口杯中的己烷成一碗含有水。添加WA之三小心入空烧杯中淬火残留的锂。 </li><li>冲洗和擦拭，其中锂被切断水的过程的其余部分继续前引擎盖。继续之前淹没在水中的这些纸巾在水槽。 </li></ol></li><li>加入约500毫升乙醚，直接从溶剂净化系统收集，通过套管转移反应烧瓶中。 </li><li>附加的烘箱中干燥回流冷凝器装有惰性气体侧臂加料漏斗和玻璃塞的三颈烧瓶中。放置一个塑料碗反应下方设置在烧瓶破裂的情况。 </li><li>添加2-溴-2-丁烯5.50g（29.0克，0.218摩尔），其已在4埃分子筛干燥过夜，以通过注射器加料漏斗。 </li><li>在5分钟的过程中添加2-溴-2-丁烯滴加大约3-4毫升，开始反应，随后回流下发生，该溶液变得浑浊。如果根10-15分钟的搅拌后，自身不会发生TLE回流，然后轻轻地用热暖烧瓶 枪，二，三分钟，直到回流下得以实现。这通常是足够的，以引发反应。 注意:即使在反应不会立即发起，控制加入2-溴-2-丁烯的关键是要保持在控制下的反应。 </li><li>添加在加料漏斗滴加90分钟的时间内将2-溴-2-丁烯的其余部分在维持整个时间周期温和回流的速率。将反应混合物将变成浅绿色。 </li><li>注射器乙酸乙酯（40.0mmol克，0.454摩尔），其已在4埃分子筛干燥过夜，和2-溴-2-丁烯（103.85克，0.782摩尔）的混合物放入加料漏斗中。该混合物添加到该反应以足够的速率，以保持在四个小时的过程中的受控但剧烈回流。 </li><li>加入完成后，注射器少量的乙酸乙酯（2.71克，0.0308摩尔）放入加料漏斗中，逐滴加入到在5分钟内将反应。该混合物将混浊橙/黄色由这些添加的结束。使反应在环境温度下搅拌过夜。 </li></ol></li><li> 第二天，替换用橡胶隔膜的加料漏斗。 <ol><li>在氩逆流，取下隔垫，用干钳抢到了一块未反应的锂。以回收尽可能多的产品成为可能，与来自洗涤瓶乙醚快速冲洗锂丝，并使溶液滴回反应容器中。然后将锂片添加到500mL烧杯充满250毫升水。 注意:锂件应单独加入到烧杯中，并在带材应该允许另一个在加入之前，充分反应。这最小化给出的淬火亲期间产生的H 2的显著量发生火灾的危险塞斯。 注:其他方法以猝灭过量的锂，如小心加入到异丙醇，也工作，但需要显著更长的时间，以充分消耗过量的锂。 </li><li> 1.3.1重复，直到所有的大块锂淬火，应要求在给定规模的60-90分钟。 </li><li>同时仍然在氩气下，加入饱和氯化铵溶液（250毫升）缓慢地滴加至搅拌的反应混合物在一小时的过程中，骤冷反应混合物和任何小块未反应锂。在反应过程中可能会轻轻地回流，并变得更加难以搅基于固体的形成。继续加入，直到沉淀的层在烧瓶底部完全溶解，形成了限定水层。 </li><li>使反应冷却30分钟后加入溶液的已完成。 </li><li>倒入烧瓶的内容到1L分液漏斗中，分离出乙醚层。 </li><li>提取用乙醚三个150毫升的部分水层。 </li><li>结合所有四个乙醚层并旋转蒸发至约75-100毫升的体积。 </li></ol></li></ol> 2. 1,2,3,4,5-五甲基环戊二烯的合成（的Cp * H） <ol><li> 附加的烘箱中干燥500mL三颈圆底烧瓶中，将惰性气体的气流下配有回流冷凝器和搅拌棒，向舒伦克线。 <ol><li>充电用对甲苯磺酸一水合物的烧瓶（8.70克，0.0457摩尔）。 </li><li>套管约50毫升乙醚到固体。 </li><li>在惰性气体下逆流，附加一个烘干的加液漏斗向反应设置。 </li><li>充电漏斗与3,4,5-三甲基-2,5- heptadien -4-醇/乙醚将来自步骤1的浓缩物。 </li><li>浓缩物滴添加到搅拌的浆料中，保持温和的回流，经1小时的过程。让反应搅拌为在加入后的额外1小时就完成了。 </li><li>将反应混合物倾入300毫升含碳酸钠4.59克（0.0433摩尔）的饱和碳酸氢钠溶液中。 </li><li>转移烧瓶的内容到1L分液漏斗中，分离出乙醚层。提取用乙醚三个100毫升的部分水层。 </li><li>结合的四个乙醚层，并用硫酸镁干燥两小时。 </li><li>过滤混合物并旋转蒸发仪下来的液体，直到〜75-100毫升物质遗存。在此阶段，该浓缩物可以存储在净身翌日过夜现有的冰箱。 </li></ol></li><li> 传送将浓缩到装有搅拌棒的烘箱中干燥，圆底烧瓶中。此烧瓶连接到配备有另一个100mL圆底烧瓶中的烘箱中干燥转移歧管。 <ol><li>酷接收瓶冰而淹没精矿在环境温度水浴中。 </li><li>适用动态真空的设置，同时搅拌该浓缩物，30〜60分钟，以除去任何残留的乙醚。 </li><li>密封该转移设置和切换浴接收烧瓶在干冰/丙酮浆液中，同时浸没在温水浴浓缩。允许陷阱到陷阱蒸馏一边搅拌，一边2-3小时的过程中，注意定期刷新真空（每15-20分钟），而浴场也超过了同一时期监测继续进行。 注:转移后，的Cp * H 39.0克（0.286摩尔，基于2-溴-2-丁烯58％）可被分离，为浅黄色油状物。 </li></ol></li></ol> 3. [*的Cp的RuCl 2] 2 29合成<ol><li> 充电钌（III）三水合物1.00克（3.95毫摩尔）的烘箱中干燥装有惰性气体上的Schlenk线流下搅拌棒100毫升的Schlenk烧瓶中。 </strong&gt;的<ol><li>套管转移50毫升甲醇中，用镁干燥，并先蒸馏来使用，在固体并搅拌30分钟。 </li><li>过滤通过一个烘箱干燥空气自由过滤漏斗在惰性气体下的溶液，充满烘箱中干燥硅藻土一英寸，向配备有搅拌棒另一个100毫升的Schlenk烧瓶中。 </li><li>除去游离的空气过滤器漏斗并用隔膜替换。 </li><li>通过注射器添加的Cp * H（1.20克，8.81毫摩尔），附加的惰性气体的气流下装有惰性气体侧臂适配器的烘箱中干燥回流冷凝器。 </li><li>密封的惰性气体的气流下在Schlenk烧瓶和回流4小时侧臂。 </li></ol></li><li> 使反应冷却和惰性气体的气流下替换用玻璃塞回流冷凝器。 <ol><li>三小时除去上的Schlenk线，真空除去溶剂，干燥。烧瓶转移到手套箱。 </li><li>手套箱内部，冲洗固体用戊烷和刮个E从烧瓶的两侧固体。过滤黑色固体到中等孔隙率玻璃料，用50ml戊烷，及干燥，真空一小时冲洗。 注意:的[Cp *的RuCl 2] 2（1.53克，基于钌的63％）被分离为深色固体。表征相匹配的文献报道。 29 </li></ol></li></ol> 4.合成的[Cp * IrCl 2] 2 30 <ol><li> 充电铱（III），氯化水合物1.00克（2.60毫摩尔）的烘箱中干燥装有惰性气体上的Schlenk线流下搅拌棒100毫升的Schlenk烧瓶中。 <ol><li>套管转移50毫升甲醇中在固体。 </li><li>通过注射器添加的Cp * H（0.50克，3.67毫摩尔），附加的惰性气体的气流下装有惰性气体侧臂适配器的烘箱中干燥回流冷凝器。 </li><li>密封的Schlenk烧瓶和回流下的惰性气体流48小时侧臂。 </li></ol></li><li&gt; 允许该反应冷却和惰性气体的气流下替换用隔膜的回流冷凝器。 <ol><li>冷却在冰浴中的烧瓶中30分钟。 </li><li>过滤通过15毫升介质的孔隙率玻璃料在空气中的反应。 </li><li>用50ml乙醚冲洗并真空干燥固体两小时。 注:的[Cp * IrCl 2] 2（1.23克，基于铱59％）分离，为橙色/红色固体。表征相匹配的文献报道。 三十 </li></ol></li></ol>

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A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=sp2+C-H+activation+of+dimethyl+fumarate+by+a+[(Cp*Co)2-&#181;-(&#951;4:&#951;4-toluene)]+complex.">sp2 C-H activation of dimethyl fumarate by a [(Cp*Co)2-&#181;-(&#951;4:&#951;4-toluene)] complex.</a> Dalton Trans. 41 (26), 8190-8197 (2012).</li><li>Hung-Low, F., Krogman, J. P., Tye, J. W., Bradley, C. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Development+of+more+labile+low+electron+count+Co(I)+sources:+mild,+catalytic+functionalization+of+activated+alkanes+using+a+[(Cp*Co)2-&#181;-(&#951;4:&#951;4-arene)]+complex.">Development of more labile low electron count Co(I) sources: mild, catalytic functionalization of activated alkanes using a [(Cp*Co)2-&#181;-(&#951;4:&#951;4-arene)] complex.</a> Chem. Commun. 48 (3), 368-370 (2012).</li><li>Andjaba, J. M., Tye, J. W., Yu, P., Pappas, I., Bradley, C. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cp*Co(IPr):+synthesis+and+reactivity+of+an+unsaturated+Co(I)+complex.">Cp*Co(IPr): synthesis and reactivity of an unsaturated Co(I) complex.</a> Chem. Commun. 52, 2469-2472 (2016).</li><li>Fendrick, C. M., Schertz, L. D., Mintz, E. A., Marks, T. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Large-scale+synthesis+of+1,2,3,4,5-pentamethylcyclpentadiene.">Large-scale synthesis of 1,2,3,4,5-pentamethylcyclpentadiene.</a> Inorg. Synth. 29, 193-198 (1992).</li><li>Threlkel, R. S., Bercaw, J. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Convenient+synthesis+of+alkyltetramethylcyclopentadienes+and+phenyltetramethylcyclopentadiene.">A Convenient synthesis of alkyltetramethylcyclopentadienes and phenyltetramethylcyclopentadiene.</a> J. Organomet. Chem. 136, 1-5 (1977).</li><li>Manriquez, J. M., Fagan, P. J., Schertz, L. D., Marks, T. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=1,2,3,4,5-pentamethylcyclopentadiene.">1,2,3,4,5-pentamethylcyclopentadiene.</a> Inorg Synth. 28, 317-320 (1990).</li><li>Threlkel, R. S., Bercaw, J. E., Seidler, P. F., Stryker, J. M., Bergman, R. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=1,2,3,4,5-pentamethylcyclopentadiene.">1,2,3,4,5-pentamethylcyclopentadiene.</a> Org. Synth. 65, (1987).</li><li>Koelle, U., Kossakowski, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Di-&#181;-chloro-bis[(&#951;5-pentachlororuthenium(III)],+[Cp*RuCl2]2+and+Di-&#181;-methoxo-bis(&#951;5-pentamethylcyclomethylcyclopentadienyl)+diruthenium(II),+[Cp*RuOMe]2.">Di-&#181;-chloro-bis[(&#951;5-pentachlororuthenium(III)], [Cp*RuCl2]2 and Di-&#181;-methoxo-bis(&#951;5-pentamethylcyclomethylcyclopentadienyl) diruthenium(II), [Cp*RuOMe]2.</a> Inorg. Synth. 29, 225-228 (1992).</li><li>White, C., Yates, A., Maitlis, P. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=&#951;5-pentamethylcyclopentadienyl)rhodium+and+-iridium+compounds.">&#951;5-pentamethylcyclopentadienyl)rhodium and -iridium compounds.</a> Inorg. Synth. 29, 228-234 (1992).</li><li>Andersen, R. A., Blom, R., Boncella, J. M., Burns, C. J., Volden, H. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+thermal+average+molecular+structures+of+bis(pentamethylcyclopentadienyl)magnesium(II),+-calcium(II),+and+-ytterbium(II)+in+the+gas+phase.">The thermal average molecular structures of bis(pentamethylcyclopentadienyl)magnesium(II), -calcium(II), and -ytterbium(II) in the gas phase.</a> Acta Chem. Scand. 41A, 24-35 (1987).</li><li>Gross, J. H., 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=Liquid+injection+field+desorption/ionization+of+reactive+transition+metal+complexes.">Liquid injection field desorption/ionization of reactive transition metal complexes.</a> Anal. Bioanal. Chem. 386 (1), 52-58 (2006).</li></ol>

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在制备heptadienol混合物，它以清洁锂发起与2-溴-2-丁烯反应之前是重要的。这是通过擦去用于纸巾存储残余的矿物油，该油出现完全从表面上除去的点，通过在己烷中的烧杯任何剩余油溶解完成。作为接收和在过程中使用前不作进一步干燥，使用了己烷。因为无论是大型反应和使用过量的锂时，通过差分法称量，以确定锂的质量是足够的。它以猝灭在发动机罩的所有材料切割和称重锂，以尽量减少...

由于二茂铁的20世纪50年代发现和结构鉴定，1，2，3，4环戊二烯（CP）取代配体的有机金属化学的发展起到了至关重要的作用。这些配位体都充当为一系列金属多功能辅助支撑，导致7的激活和小分子的官能化，8，9，10，11，12，13和催化异常结构和键合的研究，5，6，包括烯烃聚合。 14,15 1,2，3,4,5-五甲基环戊为（Cp *）阴离子已被证明是在过渡和主族金属的化学一特别有价值的配体，如甲基基团赋予更大的位阻保护作用，由阴离子配体增加的电子捐款，并阻止潜在的活化的环戊二烯基环。 16，17 *的Cp配体即使在今天仍然适用，作为阴离子最近被用来支持通过红外H / D交换（III），18铑，19和共轭胺化氢转移由钛介（III）。 20 我们在CP *配位体的兴趣从访问的小分子活化钴（Ⅰ）使用的反应性源的愿望茎。 21这些研究已经导致两个Cp *钴I和Cp的代*钴I L（L = N-杂环卡宾）当量用于sp 3键和SP 2 CH键氧化加成。 22，23，24作为访问我们的Cp *钴（II）的原料必要1,2,3,4,5-五甲基环戊二烯的显著数量，我们desired厘multigram合成* H，给予的实质性商务成本配体。 两个主要的方法目前存在的Cp * H，其中每个呈现固有的技术挑战的大规模制备。由标记和他的同事开发的方法包括2,3,4,5- tetramethylcyclopent -2-烯酮随后安装使用甲基锂最后甲基组成的两步​​合成。 25的合成大规模所述，使用一个12升的反应容器中，并机械搅拌，同时还要求持续的低温在0℃冷却四天。 另一种方法最初开发通过Bercaw和同事，26后来被改编马克斯27利用了原位生成烯锂为乙酸乙酯亲核攻击产生的3,4,5-三甲基-2,5- heptadien -4-醇的异构体混合物接着进行酸介导的环化，以提供的Cp * H。这种方法的初步报告是在一个大的（3-5升）的规模进行，所需的机械搅拌。此外，使用一个显著过量的锂金属的，复杂的淬火和中间heptadienols随后后处理。该过程的后续修订比例降低的反应和锂，28的量，但在反应混合物的安全淬火仍然是一个问题。由于在锂源和纯度或2-溴-2-丁烯反应物干燥度差异再现性的烯基中的锂，的启动被进一步指出的担忧。定为prepari常用程序，这些问题NG的Cp * H，看着我们发展到配体更好地获取在中间标度（30-40克），这将规避使用专业实验室玻璃器皿及设备，提高反应的重现性和安全性，并简化后处理和净化的配体。 这里，我们报告1,2,3,4,5-五甲基环戊二烯的那合成，基于由Bercaw和同事开发了现有程序的修改。配位体的经修订的合成和纯化完成上面概述的主要目标，同时允许获得良好的产率（58％）的Cp * H的大量（39克）。该过程还提供了其他额外的益处，包括生产中间heptadienols期间过量锂的更可控的骤冷和足够的纯度的Cp * H的用于与过渡金属随后金属化的简化隔离。为了证明制备的配位体的用途，它被用于合成2的[Cp * MCL 2] 2（M= IR，RU）配合。下面概述的订正协议补充现有的程序，并提供一种更简单和更容易进入点在有机金属化学的一个普遍存在的辅助配体载体的化学性质。

<table><tbody><tr><td>&lt;strong&gt;Materials&lt;/strong&gt;</td><td></td><td></td><td></td></tr><tr><td>Lithium wire (in mineral oil)</td><td>Aldrich</td><td>278327-100G</td><td>&gt;98%</td></tr><tr><td>2-bromo-2-butene (mixture of cis/trans isomers)</td><td>Acros</td><td>200016-364&amp;nbsp;&amp;nbsp;</td><td>98%, dried over molecular sieves from an oven overnight before use</td></tr><tr><td>Hexanes</td><td>Millipore</td><td>HX0299-3</td><td>GR ACS, used as received</td></tr><tr><td>Ethyl actetate</td><td>Millipore</td><td>EX0240-3</td><td>GR ACS, dried over molecular sieves from an oven overnight before use</td></tr><tr><td>Ammonium chloride</td><td>Aldrich</td><td>213330-2.5kg</td><td>ACS Reagent</td></tr><tr><td>Diethyl ether</td><td>Millipore</td><td>EX0190-5</td><td>GR ACS, collected from a solvent purification system before use</td></tr><tr><td>Magnesium sulfate</td><td>Aldrich</td><td>793612-500g</td><td>Anhydrous, reagent grade</td></tr><tr><td>&lt;em&gt;p&lt;/em&gt;-toluene sulfonic acid monohydrate</td><td>Fisher</td><td>A320-500</td><td>ACS Certified</td></tr><tr><td>Sodium bicarbonate</td><td>Fisher</td><td>5233-500</td><td>ACS Certified</td></tr><tr><td>Sodium carbonate</td><td>Amresco</td><td>0585-500g</td><td></td></tr><tr><td>Ruthenium(III) chloride trihydrate</td><td>Pressure Chemical</td><td>4750</td><td>40% Metal</td></tr><tr><td>Iridium(III) chloride hydrate</td><td>Pressure Chemical</td><td>5730</td><td>53% Metal</td></tr><tr><td>Methanol</td><td>Avantor</td><td>3016-22</td><td>AR ACS, distilled from Mg before use</td></tr><tr><td>Pentane</td><td>J. T. Baker</td><td>T007-09</td><td>&gt;98%, dried with a solvent purification system before use</td></tr><tr><td>Chloroform-&lt;em&gt;d&lt;/em&gt;</td><td>Aldrich</td><td>151823-150G</td><td>99.8 atom % D</td></tr><tr><td>Molecular sieves 4&amp;nbsp;&amp;Aring;</td><td>Aldrich</td><td>208590-1KG</td><td>dried in an oven at 140&amp;nbsp;&amp;deg;C before use</td></tr><tr><td>Celite 545</td><td>Acros</td><td>AC34967-0025</td><td>dried in an oven at 140&amp;nbsp;&amp;deg;C before use</td></tr><tr><td>&lt;strong&gt;Name&lt;/strong&gt;</td><td>&lt;strong&gt;Company&lt;/strong&gt;</td><td>&lt;strong&gt;Catalog Number&lt;/strong&gt;</td><td>&lt;strong&gt;Comments&lt;/strong&gt;</td></tr><tr><td>&lt;strong&gt;Equipment&lt;/strong&gt;</td><td></td><td></td><td></td></tr><tr><td>Schlenk line, with vacuum and inert gas manifolds</td><td>Custom</td><td>NA</td><td>Used in Preps 1-4</td></tr><tr><td>Solvent transfer manifold</td><td>Chemglass</td><td>AF-0558-01</td><td>Used in 2.2</td></tr><tr><td>Airfree filter funnel</td><td>Chemglass</td><td>AF-0542-22</td><td>Used in 3.1.3</td></tr><tr><td>Glovebox</td><td>Vacuum Atmospheres</td><td>OMNI</td><td>Used in 3.2.2</td></tr></tbody></table>

accessing valuable ligand supports for transition metals: a modified, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene

1,2,3,4,5-五甲基环戊二烯为（Cp * H）的一个可靠的，中间规模制备提出的基础上，从初始2-溴-2-丁烯锂化，随后通过酸介导的二烯醇环化派生现有协议的修改。配位体的经修订的合成和纯化避免使用机械搅拌的同时仍允许访问以良好的收率（58％）的Cp * H的显著量（39克）。该过程还提供了其他额外的益处，包括生产中间heptadienols期间过量锂的更可控的骤冷和足够的纯度的Cp * H的用于与过渡金属金属取代的简化隔离。该配体随后被用于合成的[Cp * MCL 2] 2配合物既铱和钌的证明* H制备和由我们的方法纯化的Cp的效用。本文介绍的步骤提供了一个无所不在的辅助配体燮得以大量端口中的有机金属化学中使用，同时减少对专门的实验室设备的需要，从而提供了一种更简单和更方便入口点1,2,3,4,5-五甲基环戊二烯的化学。

上述的Cp * H合成所述的协议依赖于三个步骤过程通过Bercaw和同事开发和商标改性（ 图1）的变形例。空气敏感烯基锂在原位通过锂/卤素交换反应而制备由顺式和反式 -2-丁烯的混合物，随后用乙酸乙酯淬灭以制备heptadienols的异构体混合物。该混合物可以不经进一步纯化即可使用的酸介导的环化，以提供单所需产物中，Cp * H。 <p class="jove_co...

Watch this Scientific Journal Video about Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene at JoVE.com

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

1,2,3,4,5-五甲基环戊二烯（的Cp * H）的可靠，中间规模制备呈现。为配位体的合成和纯化的订正协议最小化了专门的实验室设备的需要，同时简化反应workups和产物纯化。的Cp * H中的[Cp * MCL 2]的合成中的应用也被描述2复合物（M =钌，铱）。

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 ...

accessing-valuable-ligand-supports-for-transition-metals-modified

Universidad San Sebastian

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Organic Chemistry

Chemistry

Unit 1

Reactions of Alkenes

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10.3K 次观看.  Mount St. Mary's University.  1,2,3,4,5-五甲基环戊二烯（的Cp * H）的可靠，中间规模制备呈现。为配位体的合成和纯化的订正协议最小化了专门的实验室设备的需要，同时简化反应workups和产物纯化。的Cp * H中的[Cp * MCL 2]的合成中的应用也被描述2复合物（M =钌，铱）。 

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

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 &#176;C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 &#176;C make 1 to one of the most attractive and greenest Heck catalysts available.
We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 &#176;C and show that this catalyst is suitable for its use in organic syntheses.

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1) is an easy accessible, cheap, and air stable, but highly active Heck catalyst with an excellent functional group tolerance that efficiently operates under mild reaction conditions to give the coupling products in very high yields.

Mizoroki-哎呀交叉偶联反应由二氯{双[1,1&#39;，1&#39;&#39;  - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family ...

科研

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 ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

一个水溶性金属 - 有机络合物阵列合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

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 ...

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of &#945;-Imino &#947;-Lactones and Alkylidene Pyrazolones

Bispirocyclic scaffolds are one of the important structural subunits in many natural products that exhibit diverse and attractive biological activities. Recently, we have developed an efficient organocatalytic strategy, which provides facile access to a variety of enantiomerically enriched bispiro[&#947;-butyrolactone-pyrrolidin-4,4&#39;-pyrazolone] skeletons. In this paper, we demonstrate a detailed protocol for the asymmetric synthesis of drug-like bispirocyclic compounds with two spirocyclic carbon centers via an organocatyltic 1,3-dipolar cycloaddition reaction. Spirocyclization synthons &#945;-imino &#947;-lactones and alkylidene pyrazolones are prepared first, which are then subjected to a cycloaddition reaction in the presence of a bifunctional squaramide organocatalyst to afford the desired bispirocycles in high yields and excellent stereoselectivities. Chiral high-performance liquid chromatography (HPLC) is carried out to determine the enantiomeric purity of the products, and the d.r. value is examined by proton nuclear magnetic resonance (1H NMR). The absolute configuration of the product is assigned according to an X-ray crystallographic analysis. This synthetic strategy allows scientists to prepare a diversity of bispirocyclic scaffolds in high yields and excellent diastereo- and enantioselectivities.

Enantiomerically enriched bispiro[&#947;-butyrolactone-pyrrolidin-4,4&#39;-pyrazolone] skeletons are asymmetrically synthesized through a simple organocatalytic 1,3-dipolar cycloaddition reaction.

α-伊米诺γ-乳胶酮和阿基地利酮吡唑酮有机催化环加花法高效构建药物样双环脚手架

Bispirocyclic scaffolds are one of the important structural subunits in many natural products that exhibit diverse and attractive biological activities. ...

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the activation of a broad variety of organic halides, including unactivated ones. These can then participate in various radical transformations such as reduction and cyclization reactions, as well as in the direct arylation of several (hetero)arenes. These transformations provide a straightforward access to a range of small molecules of interest in synthetic chemistry, as well as to biologically active natural products. Altogether, [(DPEPhos)(bcp)Cu]PF6 acts as a convenient photoredox catalyst which appears to be an attractive, cheap and complementary alternative to the state-of-the-art iridium- and ruthenium-based photoredox catalysts. Here, we report a detailed protocol for the synthesis of [(DPEPhos)(bcp)Cu]PF6, as well as NMR and spectroscopic characterizations, and we illustrate its use in synthetic chemistry for the direct arylation of (hetero)arenes and radical cyclization of organic halides. In particular, the direct arylation of N-methylpyrrole with 4-iodobenzonitrile to afford&#160;4-(1-methyl-1H-pyrrol-2-yl)benzonitrile and the radical cyclization of N-benzoyl-N-[(2-iodoquinolin-3-yl)methyl]cyanamide to afford natural product luotonin A are detailed. The scope and limitations of this copper-based photoredox catalyst are also briefly discussed.

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Detailed and general protocols are presented for the synthesis of [(DPEPhos)(bcp)Cu]PF6, a general copper-based photoredox catalyst, and for its use in synthetic chemistry for the direct arylation of C-H bonds in (hetero)arenes and radical cyclization of organic halides.

[(Dpepphos) (bcp) Cu]PF6: 一种通用的、广泛适用的铜基光氧催化剂

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the ...

Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyl(tropone)iron

aza-Michael adducts of tricarbonyl(tropone)iron are synthesized by two different methods. Primary aliphatic amines and cyclic secondary amines participate in a direct aza-Michael reaction with tricarbonyl(tropone)iron under solvent-free conditions. Less nucleophilic aniline derivatives and more hindered secondary amines add efficiently to the cationic tropone complex formed by protonation of tricarbonyl(tropone)iron. While the protocol utilizing the cationic complex is less efficient overall for accessing the aza-Michael adducts than the direct, solvent-free addition to the neutral complex, it allows the use of a broader range of amine nucleophiles. Following protection of the amine of the aza-Michael adduct as a tert-butyl carbamate, the diene is decomplexed from the iron tricarbonyl fragment upon treatment with cerium(IV) ammonium nitrate to provide derivatives of 6-aminocyclohepta-2,4-dien-1-one. These products can serve as precursors to diverse compounds containing a seven-membered carbocyclic ring. Because the demetallation requires protection of the amine as a carbamate, the aza-Michael adducts of secondary amines cannot be decomplexed using the protocol described here.

Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyltroponeiron

Representative experimental procedures for the addition of amine nucleophiles to tricarbonyl(tropone)iron and subsequent demetallation of the resulting complexes are presented in detail.

通过三碳基(特罗酮)铁制备6-氨基环丙烯-2,4-dien-1-1衍生物

aza-Michael adducts of tricarbonyl(tropone)iron are synthesized by two different methods. Primary aliphatic amines and cyclic secondary amines participate ...

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of the reaction site in metal-organic framework (MOF)&#8211;based catalysts in an enantioselective catalytic reaction system. Therefore, a method of validating the reaction site of MOF-based catalysts is necessary to investigate this issue. Substrate size discrimination by pore size was accomplished by comparing the substrate size versus the reaction rate in two different types of carbonyl-ene reactions with two kinds of MOFs. The MOF catalysts were used to compare the performance of the two reaction types (Zn-mediated stoichiometric and Ti-catalyzed carbonyl-ene reactions) in two different media. Using the proposed method, it was observed that the entire MOF crystal participated in the reaction, and the interior of the crystal pore played an important role in exerting chiral control when the reaction was stoichiometric. Homogeneity of the chiral environment of MOF catalysts was established by the size control method for a particle used in the Zn-mediated stoichiometric reaction system. The protocol proposed for the catalytic reaction revealed that the reaction mainly occurred on the catalyst surface regardless of the substrate size, which reveals the actual reaction sites in MOF-based heterogeneous catalysts. This method for reaction site validation of MOF catalysts suggests various considerations for developing heterogeneous enantioselective MOF catalysts.

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

Here, we present a protocol for active site validation of metal-organic framework catalysts by comparing stoichiometric and catalytic carbonyl-ene reactions to find out whether a reaction takes place on the inner or outer surface of metal-organic frameworks.

使用气性金属-有机框架 （MoF） 开发异构异构选择性催化剂

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of ...

Structure Of Ferrocene

Source: Tamara M. Powers, Department of Chemistry, Texas A&#38;M University&#160;
In 1951, Kealy and Pauson reported to Nature the synthesis of a new organometallic compound, ferrocene.1&#160;In their original report, Pauson suggested a structure for ferrocene in which the iron is singly bonded (sigma bonds) to one carbon atom of each cyclopentadiene ligand (Figure 1, Structure I).1,2,3&#160;This initial report led to wide-spread interest in the structure of ferrocene, and many leading scientists participated in the structure elucidation of this interesting new molecule. Wilkinson and Woodward were quick to suggest an alternative formulization where the iron is &#34;sandwiched&#34; between two cyclopentadiene ligands, with equal binding to all 10 carbon atoms (Figure 1, Structure II).4&#160;Here, we will synthesize ferrocene and decide, based on experimental data (IR and 1H NMR), which of these structures is observed. In addition, we will study the electrochemistry of ferrocene by collecting a cyclic voltammogram. In the course of this experiment, we introduce the 18-electron rule and discuss valence electron counting for transition metal complexes.
<img alt="Figure 1" src="/files/ftp_upload/10347/10347fig1v2.jpg" /> 
Figure 1. Two proposed structures of ferrocene.

Structure Determination of Ferrocene-an Organometallic Complex

二茂铁结构

Source: Tamara M. Powers, Department of Chemistry, Texas A&#38;M University&#160;
In 1951, Kealy and Pauson reported to Nature the synthesis of a new ...

教育

JoVE Science Education

无机化学

Molecular Orbital (MO) Theory

Source: Tamara M. Powers, Department of Chemistry, Texas A&#38;M University
This protocol serves as a guide in the synthesis of two metal complexes featuring the ligand 1,1&#39;-bis(diphenylphosphino)ferrocene (dppf): M(dppf)Cl2, where M = Ni or Pd. While both of these transition metal complexes are 4-coordinate, they exhibit different geometries at the metal center. Using molecular orbital (MO) theory in conjunction with 1H NMR and Evans method, we will determine the geometry of these two compounds.

Molecular Orbital MO Theory: Predicting Geometry of Transition Metal Complexes

分子轨道 (MO) 理论

Source: Tamara M. Powers, Department of Chemistry, Texas A&#38;M University
This protocol serves as a guide in the synthesis of two metal complexes ...

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

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Mizoroki-哎呀交叉偶联反应由二氯{双[1,1'，1'' - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

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

一个水溶性金属 - 有机络合物阵列合成

钯

α-伊米诺γ-乳胶酮和阿基地利酮吡唑酮有机催化环加花法高效构建药物样双环脚手架

[(Dpepphos) (bcp) Cu]PF₆: 一种通用的、广泛适用的铜基光氧催化剂

通过三碳基(特罗酮)铁制备6-氨基环丙烯-2,4-dien-1-1衍生物

使用气性金属-有机框架（MoF）开发异构异构选择性催化剂

二茂铁结构

分子轨道 (MO) 理论

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

摘要

探索更多视频

此视频中的章节

Mizoroki-哎呀交叉偶联反应由二氯{双[1,1'，1'' - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

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

一个水溶性金属 - 有机络合物阵列合成

钯

α-伊米诺γ-乳胶酮和阿基地利酮吡唑酮有机催化环加花法高效构建药物样双环脚手架

[(Dpepphos) (bcp) Cu]PF6: 一种通用的、广泛适用的铜基光氧催化剂

通过三碳基(特罗酮)铁制备6-氨基环丙烯-2,4-dien-1-1衍生物

使用气性金属-有机框架 （MoF） 开发异构异构选择性催化剂

二茂铁结构

分子轨道 (MO) 理论

[(Dpepphos) (bcp) Cu]PF₆: 一种通用的、广泛适用的铜基光氧催化剂

使用气性金属-有机框架（MoF）开发异构异构选择性催化剂