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
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

We are grateful to the National Science Foundation (CHE-1300508) and Mount St. Mary's University (Startup and Summer Faculty Development) for generous support of this work. Ben Rupert (University of Delaware, Mass Spectrometry Facility) is acknowledged for LIFDI mass spectral analyses.

1. Synthesis of an Isomeric Mixture of 3,4,5-Trimethyl-2,5-heptadien-4-ols
<ol>
	<li>Fill an oven dried, 500 mL beaker with 200 mL of hexanes and cover with an oven dried watch glass.
	<ol>
		<li>In an empty hood, use clean scissors to cut half inch pieces of lithium wire. Wipe each lithium piece on a paper towel to remove excess mineral oil, until all oil appears to be removed from the metal&#39;s surface, and place in the beaker containing hexanes.</li>
		<li>Fill an oven dried, 250 mL beaker with 10...

<ol>
	<li>Kealy, T. J., Pauson, P. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+new+type+of+organo-iron+compound.">A new type of organo-iron compound.</a> Nature. 168, 1039-1040 (1951).</li><li>Wilkinson, G., Rosenblum, M., Whiting, M. C., Woodward, R. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+structure+of+iron+bis-cyclopentadienyl.">The structure of iron bis-cyclopentadienyl.</a> J. Am. Chem. Soc. 74, 2125-2126 (1952).</li><li>Fischer, E. O., Pfab, W. Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cyclopentadien-Metallkomplexe,+ein+neuer+Typ+metallorganischer+Verbindungen.">Cyclopentadien-Metallkomplexe, ein neuer Typ metallorganischer Verbindungen.</a> Z. Naturforsch. 76, 377-379 (1952).</li><li>Pauson, P. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ferrocene-how+it+all+began.">Ferrocene-how it all began.</a> J. Organomet. Chem. 637-639, 3-6 (2001).</li><li>Lauher, J. W., Hoffmann, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structure+and+chemistry+of+bis(cyclopentadienyl)-MLn+complexes.">Structure and chemistry of bis(cyclopentadienyl)-MLn complexes.</a> J. Am. Chem. Soc. 98, 1729-1742 (1976).</li><li>Resa, I., Carmona, E., Gutierrez-Puebla, E., Monge, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Decamethyldizincocene,+a+stable+compound+of+Zn(I)+with+a+Zn-Zn+bond.">Decamethyldizincocene, a stable compound of Zn(I) with a Zn-Zn bond.</a> Science. 305, 1136-1138 (2004).</li><li>Brintzinger, H., 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=Nature+of+so-called+titanocene,+(C10H10Ti)2.">Nature of so-called titanocene, (C10H10Ti)2.</a> J. Am. Chem. Soc. 92, 6182-6185 (1970).</li><li>King, R. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Some+applications+of+metal+carbonyl+anions+in+the+synthesis+of+unusual+organometallic+compounds.">Some applications of metal carbonyl anions in the synthesis of unusual organometallic compounds.</a> Acc. Chem. Res. 3, 417-427 (1970).</li><li>Chirik, P. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Group+4+transition+metal+sandwich+complexes:+still+fresh+after+almost+60+years.">Group 4 transition metal sandwich complexes: still fresh after almost 60 years.</a> Organometallics. 29, 1500-1517 (2010).</li><li>Bengali, A. A., Schultz, R. H., Moore, C. B., 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=Activation+of+the+C-H+bonds+in+neopentane+and+neopentane-d12+by+(&#951;5-C5(CH3)5)Rh(CO)2:+Spectroscopic+and+temporal+resolution+of+rhodium-krypton+and+rhodium-alkane+complex+intermediates.">Activation of the C-H bonds in neopentane and neopentane-d12 by (&#951;5-C5(CH3)5)Rh(CO)2: Spectroscopic and temporal resolution of rhodium-krypton and rhodium-alkane complex intermediates.</a> J. Am. Chem. Soc. 116, 9585-9589 (1994).</li><li>Shima, T., Hu, S., Luo, G., Kang, X., Luo, Y., Hou, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dinitrogen+cleavage+and+hydrogenation+by+a+trinuclear+titanium+polyhydride+complex.">Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex.</a> Science. 340, 1549-1552 (2013).</li><li>Negishi, E. -. I., Takahashi, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Alkene+and+alkyne+complexes+of+zirconocene.+Their+preparation,+structure,+and+novel+transformations.">Alkene and alkyne complexes of zirconocene. Their preparation, structure, and novel transformations.</a> Bull. Chem. Soc. Jpn. 71, 755-769 (1998).</li><li>Rosenthal, U., Burlakov, V. V., Arndt, P., Baumann, W., Spannenberg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+titancocene+complex+of+bis(trimethylsilyl)acetylene:+Synthesis,+structure,+and+chemistry.">The titancocene complex of bis(trimethylsilyl)acetylene: Synthesis, structure, and chemistry.</a> Organometallics. 22, 884-900 (2003).</li><li>Jordan, R. F., Bradley, P. K., LaPointe, R. E., Taylor, D. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cationic+zirconium+catalysts+for+carbon-carbon+bond+forming+chemistry.">Cationic zirconium catalysts for carbon-carbon bond forming chemistry.</a> New J. Chem. 14, 505-511 (1990).</li><li>Ewen, J. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Symmetry+rules+and+reaction+mechanisms+of+Ziegler-Natta+catalysts.">Symmetry rules and reaction mechanisms of Ziegler-Natta catalysts.</a> J. Mol. Catal. 128, 103-109 (1998).</li><li>Manriquez, J. M., 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=Preparation+of+a+dinitrogen+complex+of+bis(pentamethylcyclopentadienyl)zirconium(II).+Isolation+and+protonation+leading+to+the+stoichiometric+reduction+of+dinitrogen+to+hydrazine.">Preparation of a dinitrogen complex of bis(pentamethylcyclopentadienyl)zirconium(II). Isolation and protonation leading to the stoichiometric reduction of dinitrogen to hydrazine.</a> J. Am. Chem. Soc. 96, 6229-6230 (1974).</li><li>Brintzinger, H. H., 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=Bis(pentamethylcyclopentadienyl)titanium(II).+Isolation+and+reactions+with+hydrogen,+nitrogen,+and+carbon+monoxide.">Bis(pentamethylcyclopentadienyl)titanium(II). Isolation and reactions with hydrogen, nitrogen, and carbon monoxide.</a> J. Am. Chem. Soc. 93, 2045-2046 (1971).</li><li>Lehman, M. C., Gary, J. B., Boyle, P. D., Sanford, M. S., Ison, E. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+solvent+and+ancillary+ligands+on+the+catalytic+H/D+exchange+reactivity+of+Cp*IrIII(L)+complexes.">Effect of solvent and ancillary ligands on the catalytic H/D exchange reactivity of Cp*IrIII(L) complexes.</a> ACS Catal. 3, 2304-2310 (2013).</li><li>Pitman, C. L., Finster, O. N. L., Miller, A. J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cyclopentadiene-mediated+hydride+transfer+from+rhodium+complexes.">Cyclopentadiene-mediated hydride transfer from rhodium complexes.</a> Chem. Commun. 52, 9105-9108 (2016).</li><li>Tarantino, K. T., Miller, D. C., Callon, T. A., Knowles, R. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Bond-weakening+catalysis:+Conjugate+aminations+enabled+by+the+soft+homolysis+of+strong+N-H+bonds.">Bond-weakening catalysis: Conjugate aminations enabled by the soft homolysis of strong N-H bonds.</a> J. Am. Chem. Soc. 137, 6440-6443 (2015).</li><li>Bolig, A. D., Brookhart, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Activation+of+sp3+C-H+bonds+with+cobalt(I):+Catalytic+synthesis+of+enamines.">Activation of sp3 C-H bonds with cobalt(I): Catalytic synthesis of enamines.</a> J. Am. Chem. Soc. 129, 14544-14545 (2007).</li><li>Hung-Low, F., Tye, J. W., Cheng, S., 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=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>

During preparation of the heptadienol mixture, it is important to clean the lithium prior to initiating the reaction with the 2-bromo-2-butene. This is accomplished by wiping off residual mineral oil used for storage on paper towels, to the point that the oil appears fully removed from the surface, and by dissolving any remaining oil in the beaker of hexanes. The hexanes were used as received and not further dried before use in the procedure. Because of both the large scale of the reaction and an excess of lithium used, ...

1950&#39;lerde Ferrocenenin keşif ve yapısal aydınlatılması yana, 1, 2, 3, 4 siklopentadienil (Cp) ikame ligandlar organometalik kimya gelişiminde hayati bir rol oynamıştır. Bu ligandlar, sıra dışı ve yapının çalışmaları, 5, 6, 7 aktivasyonu ve küçük moleküllerin işlevselleştirilmesi, 8, 9, 10, 11, 12, 13 ve kataliz yol metallerin bir dizi için çok yönlü bir yardımcı destek olarak hizmet etmiş olefin polimerizasyon dahil olmak üzere. 14, 15 1,2, 3,4,5-pentametilsiklopentadienil (Cp *) anyon metil grupları daha sterik koruma kazandırabileceği gibi, geçiş ve ana grubu metal kimya özellikle değerli ligand olduğu kanıtlanmıştır anyonik ligand tarafından elektron bağış artmış ve potansiyel aktivasyonunu bloke etti siklopentadienil halkasının. 16 anyon son zamanlarda Ir H / D değişimi desteklemek için kullanılmıştır olarak, 17 Cp * ligand, bugün bile ilgili kalır (III), Ti aracılık Rh, 19 ve eşlenik aminleşmeler tarafından 18 hidrür transferi (III). 20 Cp *, ligand ilgi alanımız küçük molekül aktivasyonunda kullanılmak için kobalt (I) &#39;in reaktif kaynaklarına erişmek için arzu kaynaklanmaktadır. 21 Bu çalışmalar, hem Cp * Co I ve Cp elde edilmesiyle sonuçlanmıştır * CO I L (L = N-heterosiklik karben) sp3 kullanım için benzerleri vesp 2 CH bağ oksidatif eklenmesi. Başlangıç malzemeleri 1,2,3,4,5-pentamethylcyclopentadiene belirgin miktarlarda gerektiren eden Cp * Co (II) erişim gibi 22, 23, 24, biz, büyük bir ticari maliyeti göz önüne alındığında cP multigram sentezi * H istenilen ligand. İki büyük yöntemler şu içsel teknik zorluklar ortaya her biri Cp * H, büyük çapta üretimi için mevcuttur. Marks ve arkadaşları tarafından geliştirilen bir prosedür metil lityum kullanarak nihai metil grubu yüklenmesi ve ardından 2,3,4,5-tetramethylcyclopent-2-enon bir iki aşamalı sentezi içerir. 25 sentezi de dört gün boyunca, 0 ° C de soğutulduktan sürekli düşük sıcaklık gerektirirken, 12 L&#39;lik tepkime kabı ve mekanik bir karıştırıcı kullanarak, büyük bir ölçekte açıklanmaktadır. Alternatif bir prosedür aslında geliştirilenBercaw ve çalışma arkadaşları tarafından 26, daha sonra 27 3,4,5-trimetil-2,5-heptadien-4-ol&#39;lerin izomerik karışım elde etmek üzere etil asetat nükleofılik saldırının bir alkenil lityum in situ üretimi kullanmaktadır, Marks adapte Cp *, H sağlamak için asit aracılı siklizasyon takip etmektedir. Bu yöntemin ilk raporlar büyük (3-5 L) ölçekte gerçekleştirilir ve mekanik karıştırma gerekli oldu. Buna ek olarak, bir lityum metal önemli bir fazlası, söndürme ve ara heptadienols arasında Takip eden işlem, karmaşık hale kullanılmıştır. Prosedürün bir sonraki revizyon reaksiyonu ve lityum, 28 miktarını ancak reaksiyon karışımının güvenli su verme bir sorun olmaya devam aşağı ölçekler. nedeniyle 2-bromo-2-büten reaktan lityum kaynağı ve saflık ve kuruyana farklılıklara alkenil lityum, başlatılmasında tekrarlanabilirliği daha endişeleri not edilir. Beton inşaat yaygın olarak kullanılan prosedürlere bu konuları göz önüne alındığındang Cp * H, biz, özel laboratuvar cam ve ekipman kullanımını engelleyecek reaksiyon tekrarlanabilirliği ve güvenliği artırmak ve tetkik ve ligand saflaştırma basitleştirmek olur bir ara ölçekte (30-40 g) ligand daha iyi erişim geliştirmek için baktım. Burada Bercaw ve arkadaşları tarafından geliştirilen mevcut prosedürün değişiklikler dayalı, 1,2,3,4,5-pentamethylcyclopentadiene o sentezini rapor. ligandın yeniden sentezi ve saflaştırılması iyi bir verimle (% 58) &#39;de Cp * H önemli miktarda (39 g) erişime izin veren ise esas amacı, yukarıda belirtilen gerçekleştirir. Prosedür, ara heptadienols üretimi sırasında fazla lityum daha kontrollü söndürme ve geçiş metalleri ile bir sonraki metalleşmeye yeterli saflıkta Cp * H basitleştirilmiş bir izolasyon dahil olmak üzere, diğer ek avantajlar sunmaktadır. Hazırlanan ligandın kullanılmasını göstermek için iki [Cp * MCI 2] 2 (M sentez için kullanılan= Ir, Ru) kompleksleri. aşağıda belirtilen yeniden protokolü mevcut prosedürler tamamlar ve organometalik kimyada her yerde bulunan bir yardımcı ligant destek kimyası daha basit ve daha kolay erişilebilir giriş noktasını sağlar.

<table border="0" cellpadding="0" cellspacing="0" width="573">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Materials</td>
			<td style="width:71px;"></td>
			<td style="width:119px;"></td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Lithium wire (in mineral oil)</td>
			<td style="width:71px;">Aldrich</td>
			<td>278327-100G</td>
			<td style="width:167px;">&#62;98%</td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:216px;">2-bromo-2-butene (mixture of cis/trans isomers)</td>
			<td style="width:71px;">Acros</td>
			<td>200016-364&#160;&#160;</td>
			<td style="width:167px;">98%, dried over molecular sieves from an oven overnight before use</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Hexanes</td>
			<td style="width:71px;">Millipore</td>
			<td style="width:119px;">HX0299-3</td>
			<td style="width:167px;">GR ACS, used as received</td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:216px;">Ethyl actetate</td>
			<td style="width:71px;">Millipore</td>
			<td style="width:119px;">EX0240-3</td>
			<td style="width:167px;">GR ACS, dried over molecular sieves from an oven overnight before use</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Ammonium chloride</td>
			<td style="width:71px;">Aldrich</td>
			<td style="width:119px;">213330-2.5kg</td>
			<td style="width:167px;">ACS Reagent</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:216px;">Diethyl ether</td>
			<td style="width:71px;">Millipore</td>
			<td style="width:119px;">EX0190-5</td>
			<td style="width:167px;">GR ACS, collected from a solvent purification system before use</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Magnesium sulfate</td>
			<td style="width:71px;">Aldrich</td>
			<td style="width:119px;">793612-500g</td>
			<td style="width:167px;">Anhydrous, reagent grade</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">p-toluene sulfonic acid monohydrate</td>
			<td style="width:71px;">Fisher</td>
			<td style="width:119px;">A320-500</td>
			<td style="width:167px;">ACS Certified</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sodium bicarbonate</td>
			<td style="width:71px;">Fisher</td>
			<td style="width:119px;">5233-500</td>
			<td style="width:167px;">ACS Certified</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sodium carbonate</td>
			<td style="width:71px;">Amresco</td>
			<td style="width:119px;">0585-500g</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Ruthenium (III) chloride trihydrate</td>
			<td style="width:71px;">Pressure Chemical</td>
			<td style="width:119px;">4750</td>
			<td style="width:167px;">40% Metal</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Iridium (III) chloride hydrate</td>
			<td style="width:71px;">Pressure Chemical</td>
			<td style="width:119px;">5730</td>
			<td style="width:167px;">53% Metal</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Methanol</td>
			<td style="width:71px;">Avantor</td>
			<td style="width:119px;">3016-22</td>
			<td style="width:167px;">AR ACS, distilled from Mg before use</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:216px;">Pentane</td>
			<td style="width:71px;">J. T. Baker</td>
			<td style="width:119px;">T007-09</td>
			<td style="width:167px;">&#62;98%, dried with a solvent purification system before use</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Chloroform-d</td>
			<td style="width:71px;">Aldrich</td>
			<td style="width:119px;">151823-150G</td>
			<td style="width:167px;">99.8 atom % D</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Molecular sieves 4&#197;&#160;</td>
			<td style="width:71px;">Aldrich</td>
			<td style="width:119px;">208590-1KG</td>
			<td style="width:167px;">dried in an oven at 140 &#176;C before use&#160;</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Celite 545</td>
			<td style="width:71px;">Acros</td>
			<td style="width:119px;">AC34967-0025</td>
			<td style="width:167px;">dried in an oven at 140 &#176;C before use&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Name</td>
			<td style="width:71px;">Company</td>
			<td style="width:119px;">Catalog Number</td>
			<td style="width:167px;">Comments</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Equipment</td>
			<td style="width:71px;"></td>
			<td style="width:119px;"></td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Schlenk line, with vacuum and inert gas manifolds</td>
			<td style="width:71px;">Custom</td>
			<td style="width:119px;">NA</td>
			<td>Used in Preps 1-4</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">Solvent transfer manifold</td>
			<td style="width:71px;">Chemglass</td>
			<td style="width:119px;">AF-0558-01</td>
			<td style="width:167px;">Used in 2.2</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">Airfree filter funnel</td>
			<td style="width:71px;">Chemglass</td>
			<td style="width:119px;">AF-0542-22</td>
			<td style="width:167px;">Used in 3.1.3</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;">Glovebox</td>
			<td style="width:71px;">Vacuum Atmospheres</td>
			<td style="width:119px;">OMNI</td>
			<td style="width:167px;">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-pentamethylcyclopentadiene (Cp * H) güvenilir bir ara ölçekte hazırlanışı asit aracılı dienol siklizasyonu ve ardından ilk olarak 2-bromo-2-büten lityasyonundan elde mevcut protokollerinde modifikasyonları göre sunulmuştur . yine de iyi bir verimle (% 58) &#39;de Cp * H önemli miktarlarda (39 gr) erişime izin veren, bağ revize sentezi ve saflaştırılması mekanik karıştırma kullanılmasını önler. Prosedür, ara heptadienols üretimi sırasında fazla lityum daha kontrollü söndürme ve geçiş metalleri ile metalleştirme için yeterli saflıkta Cp * H basitleştirilmiş bir izolasyon dahil olmak üzere, diğer ek avantajlar sunmaktadır. Ligand daha sonra Cp * H hazırlanarak metotla arıtıldı yararını göstermek için [Cp * MCL 2] iridyum ve rutenyum hem 2 kompleksleri sentezlemek için kullanıldı. Burada özetlenen prosedür her yerde yardımcı ligant sup önemli miktarda tanıyorböylece 1,2,3,4,5-pentamethylcyclopentadiene kimyasına içine daha basit ve daha erişilebilir giriş noktası sağlayan özel laboratuar ekipmanı ihtiyacını en aza indirerek liman organometalik kimyada kullanılan.

The protocol described above for Cp*H synthesis relies on modification of the three step procedure developed by Bercaw and coworkers and modified by Marks (Figure 1). The air sensitive alkenyl lithium is prepared in situ from a mixture of cis and trans-2-butene via a lithium/halogen exchange reaction and is subsequently quenched with ethyl acetate to prepare an isomeric mixture of heptadienols. The mixture can be used without further purificatio...

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

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.

Değerli Ligand Erişme Geçiş Metaller için altlıklar: 1,2,3,4,5-Pentamethylcyclopentadiene bir Modifiye, Ara Ölçeği Hazırlık

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

Research

Education

JoVE Journal

JoVE Core

Organic Chemistry

Chemistry

Unit 1

Reactions of Alkenes

SCIENTISTS IN ACTION

Bio-layer Interferometry for Measuring Kinetics of Protein-protein Interactions and Allosteric Ligand Effects

Protein-protein etkileşimleri ve Allosterik Ligand Etkileri Kinetiği Ölçüm Bio-katman Interferometri

We describe the use of Bio-layer Interferometry to study inhibitory interactions of subunit &#949;&#160;with the catalytic complex of Escherichia ...

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Intermediate Peroksitlerin yoluyla fotokimyasal ve Asit-katalize CH fonksiyonlandırmalar tarafından Antiviral tetrahidrokarbazole Türevlerinin Sentezi (CİPS)

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order ...

Transport of Surface-modified Carbon Nanotubes through a Soil Column

Bir Toprak Kolonundaki Yüzey modifiye Karbon Nanotüpler taşınması

Carbon nanotubes (CNTs) are widely manufactured nanoparticles, which are being utilized in a number of consumer products, such as sporting goods, ...

Synthesis of Ligand-free CdS Nanoparticles within a Sulfur Copolymer Matrix

Bir Kükürt Kopolimer Matrix içinde ligand-serbest CdS Nanopartiküller Sentezi

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature ...

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

bir bis-iminoguanidinium ligand ile seçici kristalleştirme ile Sülfat Ayırma

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, ...

Preparation and Evaluation of 99mTc-labeled Tridentate Chelates for Pre-targeting Using Bioorthogonal Chemistry

Preparation and Evaluation of 99mTc-labeled Tridentate Chelates for Pre-targeting Using Bioorthogonal Chemistry

Hazırlama ve Değerlendirilmesi<sup&gt; 99m</sup&gt; Bioorthogonal Kimya Kullanarak Öncesi hedeflemek için üç dişli Şelatlar Tc-etiketli

Pre-targeting combined with bioorthogonal chemistry is emerging as an effective way to create new radiopharmaceuticals. Of the methods available, the ...

Deposition of Porous Sorbents on Fabric Supports

Kumaş destekler gözenekli Sorbentler birikimi

A microwave deposition technique for silanes, previously described for production of oleophobic fabrics, is adapted to provide a fabric support material ...

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Sentez ve elektrokimyasal CO2 azaltılması için geçiş metalleri tek Atom katalizör performans karakterizasyonu

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity ...

Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

Çekirdekleşme ligand-aracılı ve Paladyum Metal nano tanecikleri gelişmesi

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution ...

Microfluidic Preparation of Liquid Crystalline Elastomer Actuators

Sıvı kristal Elastomer aktüatörler mikrosıvısal hazırlanması

This paper focuses on the microfluidic process (and its parameters) to prepare actuating particles from liquid crystalline elastomers. The preparation ...