Name: the synthesis, characterization and reactivity of a series of ruthenium n-triphosph complexes
Uploaded: 2015-04-10T14:00:00.000+00:00
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Description: Watch this Scientific Journal Video about The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes at JoVE.com

AP is grateful to Imperial College London for a PhD studentship via the Frankland Chair endowment. Johnson Matthey plc are also thanked for the loan of the precious metal salts used in this work.

Not: Bir davlumbaz, tüm sentez yürütmek ve sadece uygun güvenlik sorunları tespit edilmiştir ve tedbirler onlara karşı korumak için alınan sonra. Kişisel koruyucu ekipman laboratuvar önlüğü, eldiven ve koruyucu gözlük dahil ve her zaman giyilmelidir. N, N, 1. sentezi, N-tris (diphenylphosphinomethylene) amin, N (CH2 PPh 2) 3 (N -triphos Ph) (1) <ol><li> 200 fırında kurutulmuş ml için Schlenk şişesine bir çift manifoldu Schlenk hat üzerinde, sıralı üç vakum azot döngüsü yoluyla nitrojen altında difenil (hidroksimetilen) fosfonyum klorür 11 (6.99 gr, 24.7 mmol) ve bir yer ilave edin. </li><li> Hydroxymethene fosfini fosfonyum klorür tuzu dönüşümünü sağlamak için 1 saat süre ile oda sıcaklığında gazı giderilmiş metanol (30 mi) ve trietilamin (9.5 mi, 68.1 mmol) ilave edin ve karıştırın. Daha sonra, metanol (2 M, 4.1 mi, 8.2 mmol), gazı alınmış amonyak çözeltisi ekleme. </li><li> Geri akış altında 2 saat boyunca reaksiyon karışımını ısıtınBu süre zarfında bağ beyaz bir katı olarak çökelecektir. </li><li> N -triphos Ph bağ uygun saflıkta için kısa bir süre üzerinde havada oksidasyon kararlı olsa da, nitrojen altında kanül süzme 26 aracılığıyla çözücüyü çıkarın ve analitik olarak saf ürün elde etmek üzere gazı alınmış metanol (3 x 10 mi) ile yıkayın ve bir nitrojen atmosferi altında muhafaza edin. </li></ol> 2. N- [Ru (CO) 2 {N- (CH2 PPh 2) 3} -κ 3P] (2) <ol><li> 200 fırında kurutulmuş ml bir Schlenk şişesine, üç ardışık vakum azot döngüsü ile nitrojen altında, N -Triphos Ph (1.0 g, 1.63 mmol) ve [Ru 3 (CO) 12] (347 mg, 0.54 mmol) ve yer eklemek Çift manifoldu savurma hattı. </li><li> Kuru, gazı alınmış tolüen, 30 ml ilave edilir ve 12 saat boyunca geri akışa kadar karışım getirir. </li><li> Bu, 12 saat geri kaynatıldıktan sonra, ikinci bir Schlenk şişesine kanül yoluyla bir çözüm için filtreReaksiyon sırasında meydana metalik rutenyum az miktardaki. </li><li> Kompleksin çökelmesine neden olmak için, tuzak soğutuldu, sıvı azot ile donatılmış bir çift manifoldu Schlenk hat kullanılarak vakum altında yaklaşık 10 ml çözücü hacmini azaltır. </li><li> Tam tekrar çözüldükten oluşana kadar bir yağ banyosu içinde yavaşça (80-90 ° C) ısıtılarak bir çökelti yeniden kristalleştirilmesi, ve bir Schlenk şişesine, yağ banyosundan ısı çıkarma, ancak izin vererek, oda sıcaklığına kadar daha sonra yavaş soğutma su altında kalması. Katı, turuncu bir kristal halinde O / N bırakın. </li><li> Başka bir fırına süpernatan, kanül filtrasyon yoluyla X-ışını kırınımı için müsait turuncu kristaller bir Schlenk şişesine kuru izole edin. Daha sonra, vakumda O / N, kuru ve gazı alınmış toluen (2 x 5 mi) ve kuru olan kristaller yıkayın. Ayrı bir Schlenk şişesi içinde bir araya süpernatan ve yıkama kaydedin. </li><li> Birleştirilen yüzer ve durulama çözeltisinden kristaller ikinci bir yığın elde ediliradım 2.5 ve 2.6 için de benzer bir tekrar kristalleştirme işlemi ile reaksiyonun bazı genel verimini iyileştirmek üzere. </li><li> Hava ile temas okside karbonat kompleksi yavaş dönüşüme yol azot altında kompleksi saklayın (aşağı bakınız). </li></ol> 3. N- [Ru (CO 3) (CO) {N- (CH2 PPh 2) 3} -κ 3 P] (3) <ol><li> 200 ml&#39;lik bir Schlenk şişesine, kısmen çözülmüş turuncu bir süspansiyon oluşturmak üzere 2 (280 mg, 0.364 mmol) ve toluen içindeki 5 ml ekleyin. </li><li> 10 dakika boyunca, reaksiyon karışımı içinden saniyede 2-3 kabarcığı süspansiyon ve kabarcık oksijen içine oksijen balonu bağlanmış bir iğne yerleştirin. </li><li> Portakal renkli bir çökelti meydana geldiğinde, havada süzme ile toplayın ve havada stabil bir serbest akan bir turuncu tozu vermek üzere vakum altında toluen (2 x 5 mi) ve dietil eter (2 x 5 mi) ve kuru ile yıkanmıştır. </li><li> X-ışını diffr için müsait kristalleri büyütmek içinaksiyon, yavaş yavaş şişenin yan tükendiğinde, bu çözücü izin vererek üstünde bir şişe ve katman 3 ml tolüen içinde 3 ml diklorometan içinde 3, 100 mg çözülür. <ol><li> Kristallerinin elde edilmesi için, bu O / N bırakın. Süpernatan ayrıldı ve toluen (2 x 3 mi) ve dietil eter (2 x 3 mi) yıkanarak kristaller izole edin. Çift manifoldu Schlenk hat üzerinde vakum altında kurutulur. </li></ol></li></ol> 4. N- [Ru (H), 2 (CO) {N- (CH2 PPh 2) 3} -κ 3P] (4) <ol><li> Kuru, 20 ml 3 (763 mg, 0.953 mmol) içindeki bir çözeltisi hazırlandı, gazı alınmış THF ve pozitif bir azot basıncı (0,2 bar) altında, 100 ml otoklav Teknisyenin yüksek basınçlı reaktöre enjekte edilir. </li><li> % 100 hidrojen reaktör kafa alanı gaz değiştirme ve 2 saat boyunca karıştırılarak 100 ° C&#39;ye kadar, daha sonra oda sıcaklığında 15 bar basınç ısı. Dikkat! Tüm güvenlik prosedürleri emin olun yüksek kullanırken uyulması edilmiştirbasınç sistemleri! </li><li> Oda sıcaklığına soğutulduktan sonra, dikkatli bir şekilde, reaktör üst boşluğunda fazla hidrojen gazı boşaltma ve azot ile değiştirin. </li><li> Nitrojen altında, 100 ml&#39;lik bir Schlenk şişesine, reaksiyon çözeltisini ve kanül yoluyla bir çift manifoldu bir Schlenk hattına, filtre bağlanmasından sonra, kuru, 20 ml ile seyreltilir, metanol gazı alındı. </li><li> Sıvı nitrojen ile donatılmış bir çift manifoldu Schlenk hat kullanılarak çözücüyü vakum altında çıkarın portakal rengi bir toz vermek üzere tuzak soğutulmuştur. Kuru, gazı alınmış metanol (3 x 5 mi) ve kuru bu portakal tozu yıkayın, dietil eter (3 x 5 mi) ve vakum altında kuru gazı alındı. </li><li> X-ışını difraksiyon analizi O uygun kristaller Büyüme / N, kuru bir Eşdeğer hacimde miktarı ile kaplanmış bir 4 kuru doymuş ve gazı alınmış tolüen çözeltiden, metanol gazı alındı. </li><li> Azot altında karmaşık saklayın. </li></ol> RUH 2 (CO) {N (CH2 PPh 2) 3} -κ 3 P [5. Reaksiyonu] (4) NH 4 PF 6 ve Levulinik Asit ile <ol><li> Kuru 2 ml 4 ihtiva eden bir çözelti (48.4 mg, 65.2 umol) hazırlanması, bir fırın içinde, toluen bir Schlenk şişesine, kurutuldu ve (asetonitril (65.0 umol, 10.6 mg) NH4 PF6 karıştırılan bir çözeltisine, şırınga yoluyla 2 ekleyin gazı alınmış ml) ayrı bir fırında bir Schlenk şişesine kurutulmuştur. </li><li> 2 st için oda sıcaklığında reaksiyon karışımı karıştırılır. Sonra (ara kompleksi [RUH (CO) (MeCN) {N- (CH2 PPh 2) 3} -κ 3 P] elde tuzak, sıvı azot ile donatılmış bir çift manifoldu savurma hattı soğutulmuş kullanılarak vakum altında çözücüyü çıkarın 5). </li><li> Kuru ile yıkayın, kahverengi bir toz olarak karmaşık 5 izole edilmesi için, vakumla heksan (3 x 3 mi) ve kuru gazı alındı. </li><li> 5 0.5 ml &#39;lik bir solüsyonuna gazı alınmış, aseton-d6, 0.5 ml (93.0 mmol, 1.43 eşdeğer. 10.8 mg) levulinik asit ilave, aseton-d6 gazı alındı. Kullanarak 2 dakika boyunca reaksiyon karışımını karıştırdıktanbir girdap karıştırıcı. </li><li> Tutanak 1 H ve 30 P {1} H reaksiyonu 16 saat reaksiyonu gözlemlemek için her saat NMR spektrumları. 27 </li></ol>

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Chem. 79, 479-489 (2001).</li></ol>

The authors have nothing to disclose.

Burada bir üç dişli bir fosfin bağı sentezi ve rutenyum komplekslerinin bir dizi verimli sentetik prosedürü de tarif etmiştik. N -triphos Ph ligandı (1) kolay bir şekilde minimalistik çalışma prosedüreüne yüksek verimle elde edilebilir. Ligandlar, bu tür sentez için kullanılan bu fosfor esaslı Mannich reaksiyonu oldukça genel ve P-atomlu R-grupları farklı olan bir başka ligand türevleri için de kullanılabilir. 10-12,15-18 Ayrıca, bu sentez yönt...

Rutenyum fosfin göre kompleksleri en çok çalışılan ve kimyasal olarak çok yönlü moleküler katalizörler arasında. 1-9 Tipik olarak bu rutenyum katalizörleri kompleks elektronik, sterics, geometri ve erime dikte mono- veya bi-dentat ligandları ya da içerir ve bu derinden katalitik aktivitesi üzerine etkisi. Bunlar metal merkeze birden fazla fosfor donör daha çelat etkisi nedeniyle, metal merkezine daha fazla stabilite kazandırmak için bilindiği gibi multidentat fosfin sistemleri daha az yaygın olarak kataliz için incelenmiştir. Bu tür stabilizasyon katalizör bütünlüğünü sağlamak avantajlı olabilir sert reaksiyon koşulları (daha yüksek sıcaklık ve basınç) bu tür ligandlara kompleks stabilize edici özellikler altında, ancak, kataliz için arzu edilmeyebilir. 10-12 ve diğerleri, 13-18 karmaşık kararlılık ve yüz -COOR kazandırmak için araştırılmıştır Bu gibi bir multidentat fosfin ligand sistemidinasyon geometrileri üç fosfin kollar potansiyel üç dişli ligand oluşturan bir tepe köprü nitrojen atomuna bağlandıkları durumda, sözde N -triphos bağ dizisidir. Bu özel ligandlarına önemli özelliklerinden biri, dolayısıyla, bu alan bir fosfor hazır ikincil fosfinler gelen Mannich reaksiyonu (Şekil 1) ile sentezlenebilir kolay bir şekilde yüksek verimlerle genellikle hazırlanabilir, ve burada R gruplarının çeşitli fosfınler ve minimal çalışma-up ile. Bu metodoloji genel amacı daha sonraki katalitik uygulamalar için erişilebilir N -triphos ligandlar içeren dihidrid kompleksleri Ruthenium hangi bir uyduruk rota sunmaktır. Son zamanlarda, Ru-triphos bazlı kompleksler levulinik asit, 19,20 biyo-esterler 11,21 ve yüksek değere sahip kimyasal karbon dioksit 22 biyokütle elde edilen ürünlerin, hidrojenasyon reaksiyonları için katalizör olarak ilgi çekmektedirler. Bu avantajlı olacaktırgibi, ya da zaten bu tür N -triphos ligand olarak, erişim sentetik daha kolay olan, özellikle de rapor sistemlere göre daha aktif ya da burada Ru-triphos türevlerinin kapsamını genişletmek için. en çok çalışılan karbon merkezli analog genellikle düşük verimli sentezi muzdarip ve hazırlamak için daha uyumlu ve kolay N -triphos ligand, aksine, son derece hava duyarlı metal fosfit reaktifleri içerir. 10-18 N -triphos ligandlar sadece molibdenum, tungsten, rutenyum, rodyum, altın kompleksleri dokuz yayınlarda rapor edilmiş olan ile nispeten az araştırılmıştır kalır. Bu benzersiz bir bileşikler büyük bir sayı ile, sırasıyla, yaklaşık 50 ve 900 maddeler bulunmaktadır olan bor ve karbon-merkezli analogları, taban tabana zıttır. Biz gibi pro-kiral olefinlerin 23 asimetrik katalitik hidrojenasyonla Bununla birlikte, kompleksler N içeren -triphos bulduk uygulamaII N gibi asimetrik cyclohydroamination γ-alenil sülfonamidler -korumalı. 24 ek olarak, yarımları koordine phospholane sahip bir hacimli N -triphos ligand ile koordine edilen bir rutenyum kompleksi silan, organosilikon kimyası gelişiminde önemli bir adım olarak aktive ettiği bulunmuştur. 25 Kataliz devam eden araştırma programının bir parçası olarak, biz rutenyum N -triphos Ph ihtiva eden ön katalizörler bir dizi hazırlamak ve onların stokiyometrik tepkilerini ve katalitik potansiyelini araştırmak için çalıştı. N -triphos Ph ilk 25 yıl önce bildirilmiştir olan molibden kompleksleri, onların uygulama rağmen katalitik veya başka araştırılmamıştır. Bu çalışma, genellikle az gelişmiş olmasına rağmen, bu tür karmaşık istikrar gibi birçok arzu özelliklere sahip N -triphos iskele, uygulanabilirliğini göstermektedir. Bu yazıda sentetik rotayı ve karakterizasyonu ve raporkatalitik hidrojenleme reaksiyonlarında uygulama bulabilir rutenyum N -triphos Ph komplekslerinin bir dizi.

<table><tbody><tr><td>Methanol</td><td></td><td></td><td>Obtained from in-house solvent purification system: Innovative Technology, inc &quot;pure solv&quot; drying tower. Stored in ampules over activated molecular sieves under nitrogen.</td></tr><tr><td>Toluene</td><td></td><td></td><td></td></tr><tr><td>Diethyl Ether</td><td></td><td></td><td></td></tr><tr><td>Tetrahydrofuran (THF)</td><td></td><td></td><td></td></tr><tr><td>Acetonitrile</td><td></td><td></td><td></td></tr><tr><td>d&lt;sub&gt;6&lt;/sub&gt;-Acetone</td><td>VWR</td><td>VWRC87152.0011</td><td>Store in fridge</td></tr><tr><td>Triethylamine</td><td>Sigma-Aldrich</td><td>TO886-1L</td><td>Distilled and stored over activated molecular sieves under N&lt;sub&gt;2&lt;/sub&gt;</td></tr><tr><td>2 M Ammonia solution in methanol</td><td>Sigma-Aldrich</td><td>341428-100ML</td><td>Solution comes in a &quot;Sure-Seal&quot; bottle</td></tr><tr><td>NH&lt;sub&gt;4&lt;/sub&gt;PF&lt;sub&gt;6&lt;/sub&gt;</td><td>Sigma-Aldrich</td><td>216593-5G</td><td>Store in desiccator</td></tr><tr><td>Levulinic Acid</td><td>Acros Organics</td><td>125142500</td><td>Solid but melts close to room temperature</td></tr><tr><td>3 &amp;Aring; Molecular sieves</td><td>Alfa Aesar</td><td>LO5359</td><td>Activate by heating over night under vacuum</td></tr><tr><td>Schlenk flasks</td><td>GPE</td><td>Custom design</td><td></td></tr><tr><td>Dual-manifold Schlenk line</td><td>GPE</td><td>Custom design</td><td>Dual-manifold of i) N&lt;sub&gt;2&lt;/sub&gt; that has been passed through a silica drying column and ii) vacuum.</td></tr><tr><td>Rotary vacuum pump</td><td>Edwards</td><td>RV3 A652-01-903</td><td></td></tr><tr><td>100 ml Autoclave Engineer&#039;s high pressure reactor</td><td>Autoclave Engineer</td><td>Custon design</td><td></td></tr><tr><td>Vortex Stirrer</td><td>VWR</td><td>444-1378</td><td></td></tr></tbody></table>

the synthesis, characterization and reactivity of a series of ruthenium n-triphosph complexes

Bu yazıda, bir nitrojen atmosferi altında, metanol içinde amonyak ile hydroxylmethylene fosfin öncüsünün bir fosfor esaslı Mannich reaksiyonu yoluyla bir üç dişli fosfin ligandı, N (CH2 PPh 2) 3 (N -triphos Ph) (1) &#39;in sentezini rapor etmektedir. N -triphos pH bağ geri akış arasında, yaklaşık 1 saat sonra çözeltiden çökelir ve azot altında, basit bir kanül filtrasyon prosedürü yoluyla analitik olarak saf izole edilebilir. Geri akış altında, [Ru 3 (CO) 12] ile N -triphos Ph ligandın tepkime ligandı kompleks CO gazının yayılmasını gösteren koyu kırmızı bir çözelti elde edilir. Kompleks, [Ru (CO) 2 {N- (CH2 PPh 2) 3} -κ 3P] (2) oda sıcaklığına soğutulduktan üzerinde izole edildi ve turuncu kristaller. 31 P {1H} NMR spektrumu düşük frekansta bir karakteristik tek bir pik gösterdiserbest ligand ile karşılaştırıldığında. Oksijen ile kompleks bir 2 toluen çözeltisi reaksiyonu karbonat kompleksi [Ru (CO 3) (CO) {N- (CH2 PPh 2) 3} -κ 3P] anında çökeltilmesi ile sonuçlanmıştır (3) bir hava istikrarlı olarak Katı turuncu. Yüksek basınçlı bir reaktörde hidrojen 3 altında 15 bar Daha sonraki hidrojenleme, dihidrid kompleksi [RUH 2 (CO) {N- (CH2 PPh 2) 3} -κ 3P] (4) tam olarak X ile karakterize verdi -ray kristallografisi ve NMR spektroskopisi. Kompleksi 3 ve 4 gibi potansiyel levulinik asit (LA) ve biyo-kütleden türetilen ürünler dahil olmak üzere, hidrojenasyon reaksiyonların bir dizi için, yararlı bir katalizör ön-maddeleridir. Kompleks 4 temiz NH4 PF6 ({N- [elde Ru (CO) proton kaynağı, katkı maddesinin varlığında LA ile reaksiyona girdiği görülmüştürCH2 PPh 2) 3} -κ 3 P {CH3, CO (CH2) 2-CO 2H} -κ 2O] (PF6) (6).

N -triphos Ph ligandı (1) ve rutenyum kompleksi seriye ait: Ru (CO) 2 {N- (CH2 PPh 2) 3} -κ 3P] (2), [Ru (CO 3) (CO) N { (CH2 PPh 2) 3} -κ 3 P] (3) ve [Ru (H), 2 (CO) {N- (PPh 2 CH2) 3} -κ 3P] (4) 1 H ile karakterize edilmiştir, 13C {1H}, 30 P {1H} NM...

Watch this Scientific Journal Video about The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes at JoVE.com

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Rutenyum fosfin kompleksleri yaygın olarak sıvılaştırma homojen katalitik reaksiyonlar için kullanılmaktadır. N -triphos ligand N (CH2 PPh 2) 3 taşıyan yeni üç dişli rutenyum komplekslerinin bir dizi sentezi rapor edilmiştir. Buna ek olarak, levulinik asit ile dihidrid Ru- N -triphos kompleksinin stoikiometrik reaksiyon tarif edilmiştir.

Rutenyum bir Serisi Sentezi, Karakterizasyonu ve Tepkime<em&gt; K</em&gt; -triphos<sup&gt; Ph</sup&gt; Kompleksi

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

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Chemistry

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

12.1K Görüntüleme.  Imperial College London.  Rutenyum fosfin kompleksleri yaygın olarak sıvılaştırma homojen katalitik reaksiyonlar için kullanılmaktadır. N -triphos ligand N (CH2 PPh 2) 3 taşıyan yeni üç dişli rutenyum komplekslerinin bir dizi sentezi rapor edilmiştir. Buna ek olarak, levulinik asit ile dihidrid Ru- N -triphos kompleksinin stoikiometrik reaksiyon tarif edilmiştir. 

Video: The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

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.

Hafif reaksiyon koşulları altında paladyum - Dikloro {bis [(phosphinetriyl) tripiperidine 1,1 &#39;, 1&#39;&#39;]} katalize Mizoroki-Heck Çapraz bağlama reaksiyonları

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 ...

Kimya

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

Çekirdekli Antikanser Maddeleri olarak Platinum bispiridin tabanlı Ligandların ve kompleks Sentezlenmesi için kullanılan amid bağlantı reaksiyon

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

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.

suda çözünür bir metal-organik kompleks dizi sentezi

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.

palladyum<em&gt; K</em&gt; -Heterosiklik Karben Kompleksleri: Benzimidazolyum Tuzlarından Sentez ve Karbon-karbon Bağ Oluşturma Reaksiyonlarında Katalitik Aktivite

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

Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of this compound commences from [Ru(NH3)5Cl]Cl2 in 1 M NH4OH in a closed container, yielding a green solution. Purification is accomplished with cation-exchange chromatography. This compound is characterized and verified to be pure by UV-vis and IR spectroscopy. The mitochondrial calcium uptake inhibitory properties are assessed in permeabilized HeLa cells by fluorescence spectroscopy.

A protocol for the synthesis, purification, and characterization of a ruthenium-based inhibitor of mitochondrial calcium uptake is presented. A procedure to evaluate its efficacy in permeabilized mammalian cells is demonstrated.

Sentez ve rutenyum tabanlı mitokondrial kalsiyum alımını inhibitörü değerlendirilmesi

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of ...

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile N-(2-alkoxyvinyl)sulfonamides, which react under a variety of conditions to afford useful N- and O-containing compounds. Acid-catalyzed addition of alcohols or thiols to N-(2-alkoxyvinyl)sulfonamide-containing phthalans provides access to ketals and thioketals, respectively. Selective reduction of the vinyl group in N-(2-alkoxyvinyl)sulfonamide-containing phthalans via hydrogenation yields the corresponding phthalan in good yield, whereas reduction with sodium bis(2-methoxyethoxy)aluminumhydride generates a ring-opened phenethylamine analogue. Because the N-(2-alkoxyvinyl)sulfonamide functional group is synthetically versatile, but often hydrolytically unstable, this protocol emphasizes key techniques in preparing, handling, and reacting these pivotal substrates in several useful transformations.

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Representative experimental procedures for the synthesis of N-(2-alkoxyvinyl)sulfonamides and subsequent conversion to phthalan and phenethylamine derivatives are presented in detail.

Nhazırlanması-(2-alkoxyvinyl) N- tosyl-1,2,3-triazoles ve yerine Phthalans ve fenitilaminler sonraki dönüşüm sülfonamidler

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile ...

An In Vitro Enzymatic Assay to Measure Transcription Inhibition by Gallium(III) and H3 5,10,15-tris(pentafluorophenyl)corroles

Chemotherapy often involves broad-spectrum cytotoxic agents with many side effects and limited targeting. Corroles are a class of tetrapyrrolic macrocycles that exhibit differential cytostatic and cytotoxic properties in specific cell lines, depending on the identities of the chelated metal and functional groups. The unique behavior of functionalized corroles towards specific cell lines introduces the possibility of targeted chemotherapy.
Many anticancer drugs are evaluated by their ability to inhibit RNA transcription. Here we present a step-by-step protocol for RNA transcription in the presence of known and potential inhibitors. The evaluation of the RNA products of the transcription reaction by gel electrophoresis and UV-Vis spectroscopy provides information on inhibitive properties of potential anticancer drug candidates and, with modifications to the assay, more about their mechanism of action.
Little is known about the molecular mechanism of action of corrole cytotoxicity. In this experiment, we consider two corrole compounds: gallium(III) 5,10,15-(tris)pentafluorophenylcorrole (Ga(tpfc)) and freebase analogue 5,10,15-(tris)pentafluorophenylcorrole (tpfc). An RNA transcription assay was used to examine the inhibitive properties of the corroles. Five transcription reactions were prepared: DNA treated with Actinomycin D, triptolide, Ga(tpfc), tpfc at a [complex]:[template DNA base] ratio of 0.01, respectively, and an untreated control.
The transcription reactions were analyzed after 4 hr using agarose gel electrophoresis and UV-Vis spectroscopy. There is clear inhibition by Ga(tpfc), Actinomycin D, and triptolide.
This RNA transcription assay can be modified to provide more mechanistic detail by varying the concentrations of the anticancer complex, DNA, or polymerase enzyme, or by incubating the DNA or polymerase with the complexes prior to RNA transcription; these modifications would differentiate between an inhibition mechanism involving the DNA or the enzyme. Adding the complex after RNA transcription can be used to test whether the complexes degrade or hydrolyze the RNA. This assay can also be used to study additional anticancer candidates.

An In Vitro Enzymatic Assay to Measure Transcription Inhibition by GalliumIII and H3 5,10,15-trispentafluorophenylcorroles

Gallium(III) 5,10,15-(tris)pentafluorophenylcorrole and its freebase analogue exhibit low micromolar cell cytotoxicity. This manuscript describes an RNA transcription reaction, imaging RNA with an ethidium bromide-stained gel, and quantifying RNA with UV-Vis spectroscopy, in order to assess transcription inhibition by corroles and demonstrates a straightforward method of evaluating anticancer candidate properties.

Bir<em&gt; İn Vitro</em&gt; Enzimatik Deneyi Galyum (III) ve H Transkripsiyon İnhibisyonunu Tedbir<sub&gt; 3</sub&gt; 5,10,15-tris (pentaflüorofenil) corroles

Chemotherapy often involves broad-spectrum cytotoxic agents with many side effects and limited targeting. Corroles are a class of tetrapyrrolic ...

Biyomühendislik

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst removal via host-guest interactions. The new NHC ligand possesses an adamantyl (guest) tethered linear ethylene glycol units for hydrophobic inclusion into the cavity of a &#946;-cyclodextrin (&#946;-CD) host compound. The new NHC ligand was applied to a Ru-based olefin metathesis catalyst. The Ru catalyst demonstrated excellent activity in representative ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP) reactions in aqueous media as well as organic solvent, CH2Cl2. After the reaction was complete, the lingering Ru residue was removed from the aqueous solution with the efficiency of more than 99% (53 ppm of Ru residue) by simple filtration utilizing a host-guest interaction between insoluble silica-grafted &#946;-CD (host) and the adamantyl moiety (guest) on the catalyst. The new Ru catalyst also demonstrated high removal efficiency via extraction when the reaction is run in organic solvent by partitioning the crude reaction mixture between layers of diethyl ether and water. In this way, the catalyst stays in aqueous layer only. In organic layer, the residual Ru amount was only 0.14 ppm in the RCM reactions of diallyl compounds.

A removable water-soluble N-heterocyclic carbene (NHC) ligand in aqueous media via host-guest interaction has been developed. We demonstrated representative olefin metathesis reactions in water as well as in dichloromethane. Via either host-guest interaction or extraction, the residual ruthenium (Ru) catalyst was as low as 0.14 ppm after the reaction.

Türdeş olmayan suda çözünen Rutenyum Organik sentezde Catalyst ana bilgisayar-Konuk etkileşim yoluyla sulu ortamdan çıkarılması

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst ...

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes and determine the corresponding photochemical mechanism. Then, we describe a protocol to perform ring-opening metathesis polymerization (ROMP) in solution and in miniemulsion using this NHC-photogenerating system. To photogenerate IMes, a system comprising 2-isopropylthioxanthone (ITX) as the sensitizer and 1,3-dimesitylimidazolium tetraphenylborate (IMesH+BPh4-) as the protected form of NHC is employed. IMesH+BPh4- can be obtained in a single step by anion exchange between 1,3-dimesitylimidazolium chloride and sodium tetraphenylborate. A real-time steady-state photolysis setup is described, which hints that the photochemical reaction proceeds in two consecutive steps: 1) ITX triplet is photo-reduced by the borate anion and 2) subsequent proton transfer takes place from the imidazolium cation to produce the expected NHC IMes. Two separate characterization protocols are implemented. Firstly, CS2 is added to the reaction media to evidence the photogeneration of NHC through formation of the IMes-CS2 adduct. Secondly, the amount of NHC released in situ is quantified using acid-base titration. The use of this NHC photo-generating system for the ROMP of norbornene is also discussed. In solution, a photopolymerization experiment is conducted by mixing ITX, IMesH+BPh4-, [RuCl2(p-cymene)]2 and norbornene in CH2Cl2, then irradiating the solution in a UV reactor. In a dispersed medium, a monomer miniemulsion is first formed then irradiated inside an annular reactor to produce a stable poly(norbornene) latex.

We describe a protocol to photogenerate N-heterocyclic carbenes (NHCs) by UV irradiation of a 2-isopropylthioxanthone/imidazolium tetraphenylborate salt system. Methods to characterize the photoreleased NHC and elucidate the photochemical mechanism are proposed. The protocols for ring-opening metathesis photopolymerization in solution and miniemulsion illustrate the potential of this 2-component NHC photogenerating system.

N oluşur Carbenes Photogeneration: Photoinduced yüzük-açılış sentezde polimerizasyon uygulamada

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes ...

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis (FCLSA) on spectral data, in addition to CIE color coordinate determination and basic spectral processing. While some of the features may be found in commercial software or in programs made by&#160;academic research groups, we believe that ARL Spectral Fitting is the only application that possesses all three of the aforementioned attributes.
This program is intended as a standalone, GUI-based application for use by an average laboratory researcher without requiring any coding knowledge or proprietary software. In addition to the standalone executable hosted on ARL GitHub, the associated MATLAB files are available for use and further development.
FCLSA augments the information found in luminescence spectra, providing meaningful insight into the relationship between the ground and excited states of a photoluminescent species. This insight is achieved by modeling spectra with two versions (modes) of an equation that are characterized by either four or six parameters, depending on which mode is used. Once optimized, the value of each of these parameters can be used to gain insight into the molecule, as well as to perform further analysis (for example, the free energy content of the excited-state molecule). This application provides tools for easy by-hand fitting of imported data, as well as two methods for optimizing this fit-damped least-squares fitting, powered by the Levenberg-Marquardt algorithm, and derivative-free fitting utilizing the Nelder-Mead simplex algorithm. Furthermore, estimations of sample color can be performed and reported in CIE and RGB coordinates.

This protocol introduces Franck-Condon Lineshape Analyses (FCLSA) of emission spectra and serves as a tutorial for the use of ARL Spectral Fitting software. The open-source software provides an easy and intuitive way to perform advanced analysis of emission spectra including excited state energy calculations, CIE color coordinate determination, and FCLSA.

Franck-Condon Lineshape Analizi ve Renk Analizi ile Spektral Verileri Artırmak için Bir Uygulama Olarak ARL Spektral Uydurma

The ARL Spectral Fitting application provides a free, publicly accessible, and fully transparent method for performing Franck-Condon Lineshape Analysis ...

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