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.

Nota: Eseguire tutte le sintesi in una cappa aspirante, e solo dopo che i problemi di sicurezza del caso sono stati identificati e le misure adottate per la protezione contro di loro. Dispositivi di protezione individuale comprende un camice da laboratorio, guanti e occhiali di sicurezza e devono essere indossati in ogni momento. 1. Sintesi di N, N, N tris (diphenylphosphinomethylene) ammina, N (CH 2 PPh 2) 3 (N -triphos Ph) (1) <ol><li> Per ml asciugato in forno a 200 Vetreria Schlenk aggiungere difenil cloruro (idrossimetilene) fosfonio 11 (6,99 g, 24,7 mmol) e posto sotto azoto con tre cicli di vuoto-azoto sequenziali su una linea Schlenk dual-collettore. </li><li> Aggiungere metanolo degasato (30 ml) e trietilammina (9,5 ml, 68,1 mmol) e agitare a temperatura ambiente per 1 ora per assicurare la conversione del sale di fosfonio cloruro al fosfina hydroxymethene. Successivamente, aggiungere la soluzione di ammoniaca degasata in metanolo (2 M, 4,1 ml, 8,2 mmol). </li><li> Riscaldare la miscela di reazione per 2 ore a riflusso, Durante il quale il ligando si precipita come solido bianco. </li><li> Sebbene la N -triphos Ph ligando è stabile all&#39;ossidazione in aria su brevi periodi di tempo, per la purezza ottimale, rimuovere il solvente mediante cannula filtrazione 26 sotto azoto, e risciacquare con metanolo degasato (3 x 10 ml) per ottenere un prodotto analiticamente puro , e conservare sotto atmosfera di azoto. </li></ol> 2. Sintesi di [Ru (CO) 2 {N (CH 2 PPh 2) 3} 3 -κ P] (2) <ol><li> Per un pallone Schlenk 200 ml a forno, aggiungere N -Triphos Ph (1,0 g, 1.63 mmol) e [Ru 3 (CO) 12] (347 mg, 0,54 mmol), e posto sotto azoto con tre cicli di vuoto-azoto sequenziali su una linea a doppio collettore Schlenk. </li><li> Aggiungere 30 ml di secca, toluene da gas e portare il composto a riflusso per 12 ore. </li><li> Dopo questo 12 hr reflusso, filtrare la soluzione attraverso una cannula ad un secondo pallone a Schlenkrimuovere piccole quantità di rutenio metallico che si formano durante il corso della reazione. </li><li> Ridurre il volume di solvente a circa 10 ml sotto vuoto utilizzando una linea a doppio collettore Schlenk munito di azoto liquido trappola raffreddata, per indurre la precipitazione del complesso. </li><li> Ricristallizzare il precipitato con blando riscaldamento (80-90 ° C) in bagno d&#39;olio, fino alla completa ridissoluzione, e successivo raffreddamento lento a RT rimuovendo il calore dal bagno d&#39;olio, ma consentendo il pallone Schlenk di rimanere sommerso. Lascia O / N di dare una cristallina arancione solido. </li><li> Isolare i cristalli arancioni adatti per diffrazione di raggi X mediante cannula filtrazione del supernatante in un altro forno essiccati pallone Schlenk. Successivamente, lavare i cristalli con toluene anidro e degasato (2 x 5 ml) ed essiccare sotto vuoto O / N. Salvare il surnatante e lavaggi combinati in un pallone Schlenk separato. </li><li> Ottenere un secondo lotto di cristalli dal supernatante combinato e la soluzione di risciacquos mediante un processo simile a ricristallizzazione passi 2.5 e 2.6 per migliorare la resa complessiva di reazione. </li><li> Conservare il complesso sotto azoto come esposizione all&#39;aria porta alla lenta conversione al complesso carbonato ossidato (vedi sotto). </li></ol> 3. Sintesi di [Ru (CO 3) (CO) {N (CH 2 PPh 2) 3} 3 -κ P] (3) <ol><li> Per un pallone da 200 ml Schlenk, aggiungere 2 (280 mg, 0,364 mmol) e 5 ml di toluene per generare una sospensione arancia parzialmente disciolto. </li><li> Inserire un ago attaccato ad un palloncino di ossigeno nella sospensione e bolle di ossigeno ad una velocità di 2-3 bolle al secondo attraverso la miscela di reazione per 10 min. </li><li> Come un precipitato arancione, raccoglierlo per filtrazione in aria e lavato con toluene (2 x 5 ml) e dietil etere (2 x 5 ml) e secco sotto vuoto per dare un arancio polvere scorrevole che era stabile in aria. </li><li> Per crescere cristalli adatti per X-ray diffrazione, sciolgono 100 mg di 3 in 3 ml di diclorometano in una fiala e lo strato 3 ml toluene sopra lentamente permettendo questo solvente a correre lungo il lato del flaconcino. <ol><li> Lasciare questo O / N per ottenere cristalli. Isolare i cristalli per decantazione del surnatante, e lavare il toluene (2 x 3 ml) e dietil etere (2 x 3 ml). Secco sotto vuoto su una linea Schlenk dual-collettore. </li></ol></li></ol> 4. Sintesi di [Ru (H) 2 (CO) {N (CH 2 PPh 2) 3} 3 -κ P] (4) <ol><li> Preparare una soluzione di 3 (763 mg, 0,953 mmol) in 20 ml di asciutto, degassato THF e iniettare in un reattore da 100 ml ad alta pressione del tecnico Autoclave sotto una pressione positiva (0,2 bar) di azoto. </li><li> Cambiare il gas spazio di testa del reattore a 100% di idrogeno e pressurizzare a 15 bar a RT, allora il calore a 100 ° C con agitazione per 2 ore. Attenzione Garantire tutte le procedure di sicurezza sono state rispettate quando si utilizza altasistemi a pressione! </li><li> Dopo raffreddamento a RT, sfiatare accuratamente il gas idrogeno in eccesso nello spazio di testa del reattore e cambiare azoto. </li><li> Trasferire la soluzione di reazione ad un pallone da 100 ml Schlenk sotto azoto e, dopo aver ricollegato ad una linea a doppio collettore Schlenk, filtro mediante cannula e diluire con 20 ml di secca, degassato metanolo. </li><li> Rimuovere il solvente sotto vuoto utilizzando una linea a doppio collettore Schlenk munito di azoto liquido raffreddato trappola per dare una polvere arancione. Lavare la polvere arancione con secca, metanolo degasato (3 x 5 ml) e secco, degassato etere etilico (3 x 5 ml) e secco sotto vuoto. </li><li> Grow cristalli adatti per l&#39;analisi di diffrazione ai raggi X O / N da una soluzione toluenica saturo secco e degasata di 4 strati con una quantità Equivolume secco, degassato metanolo. </li><li> Conservare il complesso sotto azoto. </li></ol> 5. La reazione di [Ruh 2 (CO) {N (CH 2 PPh 2) 3} -κ 3 P] (4) con NH 4 PF 6 e Acid levulinico <ol><li> Preparare una soluzione di 4 (48,4 mg, 65,2 mmol) in 2 ml secco, degassata toluene in un forno essiccato beuta Schlenk, e aggiungere tramite siringa ad una soluzione agitata di NH 4 PF 6 (10,6 mg, 65,0 mmol) in acetonitrile (2 ml) in un forno separato essiccato pallone Schlenk. </li><li> Mescolare la miscela di reazione a temperatura ambiente per 2 ore. Dopo, rimuovere il solvente sotto vuoto con una linea a doppio collettore Schlenk munito di azoto liquido raffreddato trappola per dare l&#39;intermedio complesso [ruh (CO) (MeCN) {N (CH 2 PPh 2) 3} 3 -κ P] ( 5). </li><li> Lavare con secca, degassato esano (3 x 3 ml) e secco sotto vuoto per isolare complessi 5 come polvere marrone. </li><li> Ad una soluzione di 5 a 0,5 ml di acetone degassato-d 6, aggiungere l&#39;acido levulinico (10,8 mg, 93,0 mmol, 1,43 equiv.) In 0,5 ml di acetone degasato-d 6. Mescolare la miscela di reazione per 2 min usandoun agitatore vortex. </li><li> Record 1 H e 30 P {1} H NMR della reazione ogni ora per 16 ore per osservare la reazione. 27 </li></ol>

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The authors have nothing to disclose.

Qui abbiamo descritto procedure sintetiche efficienti per la sintesi di un legante tridentato fosfina ed una serie di complessi di rutenio. Il N -triphos Ph ligando (1) può essere facilmente preparato in alto rendimento con una procedura di work-up minimalista. Questa reazione Mannich base di fosforo utilizzato per sintetizzare questi tipi di leganti è del tutto generale e può essere utilizzato per altri derivati ​​ligando con R-gruppi differenti sul P-atomi. 10-12,15-18<...

Complessi basati Rutenio fosfina sono alcuni dei catalizzatori molecolari più studiati e chimicamente versatili. 1-9 Tipicamente, tali catalizzatori di rutenio contengono ligandi sia mono o bi-dentate che dettano dell&#39;elettronica, sterics, la geometria e la solubilità del complesso, e che impatto profondo sulle attività catalitica. Sistemi fosfina multidentati sono state meno ampiamente studiato per la catalisi, come sono noti per conferire maggiore stabilità sul centro metallico a causa del maggiore effetto chelato di donatori multipli fosforo sul centro metallico. Tale stabilizzazione può essere indesiderabile per catalisi, tuttavia, in condizioni severe di reazione (alte temperature e pressioni) le proprietà stabilizzanti complessi di tali ligandi può essere vantaggioso per garantire l&#39;integrità catalizzatore. Uno di questi sistemi ligando fosfina multidentati che abbiamo 10-12 e 13-18 gli altri hanno indagato per impartire stabilità del complesso e coor faccialegeometrie coordina- è la cosiddetta serie ligando N -triphos dove tre bracci fosfina sono attaccati ad un atomo di azoto apicale bridging formando un ligando potenzialmente tridentato. Una delle caratteristiche fondamentali di questi ligandi particolari è il modo facile che essi possono essere sintetizzati mediante una reazione di Mannich base di fosforo e di facile reperibilità fosfine secondarie (Figura 1), quindi fosfine con una varietà di gruppi R possono essere preparati solito in rese elevate e con il minimo work-up. L&#39;obiettivo generale di questa metodologia è quello di presentare un percorso facile attraverso il quale rutenio complessi diidruro dotate N -triphos ligandi si può accedere per le successive applicazioni catalitiche. Recentemente, complessi basati Ru-triphos hanno attirato l&#39;attenzione come catalizzatori per le reazioni di idrogenazione di biomassa prodotti derivati, come l&#39;acido levulinico, 19,20 bio-esteri 11,21 e anidride carbonica 22 a sostanze chimiche di maggior valore. Sarebbe vantaggiosodi ampliare la portata dei derivati ​​Ru-triphos che sono o come, o più attivi dei sistemi già riferito, specialmente se sono sinteticamente più facile accesso, come la N -triphos ligando. L&#39;analogo carbonio centrata più studiato soffre tipicamente da basso sintesi cedevole e coinvolge reagenti fosfuro metallo altamente aria-sensibili, a differenza della N -triphos ligando, che è più flessibile e più facile da preparare. 10-18 N -triphos ligandi rimangono relativamente sotto-indagato, con solo molibdeno, tungsteno, rutenio, rodio e oro complessi essendo stati segnalati da nove pubblicazioni. Questo è in netto contrasto con gli analoghi bóron- carbonio e centrata, per i quali vi sono circa 50 e 900 articoli, rispettivamente, con un gran numero di composti unici. Applicazione Tuttavia, -triphos N contenenti complessi hanno trovato nella idrogenazione catalitica asimmetrica di olefine pro-chirali 23 come noill cyclohydroamination come asimmetrica di N antideflagrante sulfamidici γ-allenyl. 24 Inoltre, un complesso di rutenio coordinato da ligando un ingombrante N -triphos con phospholane coordinamento frazioni è stato trovato per attivare silani, un passo fondamentale nello sviluppo della organosilicio chimica. 25 Come parte del programma di ricerca in corso nella catalisi, abbiamo cercato di preparare una serie di rutenio N -triphos precatalysts Ph e di indagare le loro reazioni stechiometrico e potenzialità catalitica. Nonostante complessi molibdeno di N -triphos Ph essendo stato segnalato più di 25 anni fa, la loro applicazione, catalitica o altrimenti non è stata studiata. Questo lavoro dimostra l&#39;applicabilità della N -triphos impalcatura, che pur essendo generalmente poco sviluppato, possiede molte caratteristiche desiderabili come stabilità del complesso. Qui riportiamo la via di sintesi e caratterizzazione di auna serie di rutenio N -triphos complessi Ph che possono trovare applicazione in reazioni di idrogenazione catalitica.

<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

Qui riportiamo la sintesi di un legante tridentato fosfina N (CH 2 PPh 2) 3 (N -triphos Ph) (1) tramite una base di fosforo reazione Mannich del precursore hydroxylmethylene fosfina con ammoniaca in metanolo sotto atmosfera di azoto. La N -triphos Ph ligando precipita dalla soluzione dopo circa 1 ora di reflusso e può essere isolato analiticamente puro mediante semplice procedura di filtrazione cannula sotto azoto. Reazione del N -triphos Ph ligando con [Ru 3 (CO) 12] a ricadere offre una soluzione rosso profondo che mostrano l&#39;evoluzione di gas CO il ligando complessazione. Cristalli arancioni del complesso [Ru (CO) 2 {N (CH 2 PPh 2) 3} 3 -κ P] (2) sono stati isolati per raffreddamento a RT. Lo spettro NMR 31 P {1 H} mostrato una caratteristica singolo picco a frequenza più bassarispetto al legante libero. Reazione di una soluzione toluenica di complesso 2 con l&#39;ossigeno portato alla precipitazione istantanea del carbonato complesso [Ru (CO 3) (CO) {N (CH 2 PPh 2) 3} 3 -κ P] (3) come stabile dell&#39;aria arancione solido. Idrogenazione successiva di 3 con 15 bar di idrogeno in un reattore ad alta pressione ha dato il complesso diidruro [RUH 2 (CO) {N (CH 2 PPh 2) 3} 3 -κ P] (4), che è stato pienamente caratterizzato da X cristallografia a raggi e spettroscopia NMR. Complessi 3 e 4 sono potenzialmente precursori di catalizzatori utili per una serie di reazioni di idrogenazione, compresi i prodotti derivati ​​da biomassa come l&#39;acido levulinico (LA). Complesso 4 è stato trovato reagire in modo pulito con LA in presenza dell&#39;additivo fonte protoni NH 4 PF 6 per dare [Ru (CO) {N (CH 2 PPh 2) 3} 3 -κ P {CH 3 CO (CH 2) 2 CO 2 H} -κ 2 O] (PF 6) (6).

La N -triphos Ph ligando (1) e la serie complesso di rutenio: Ru (CO) 2 {N (CH 2 PPh 2) 3} 3 -κ P] (2), [Ru (CO 3) (CO) {N (CH 2 PPh 2) 3} 3 -κ P] (3) e [Ru (H) 2 (CO) {N (CH 2 PPh 2) 3} 3 -κ P] (4) sono state caratterizzate tramite 1 H, 13 C {1}</...

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

Complessi di Rutenio fosfina sono ampiamente utilizzati per le reazioni catalitiche omogenee quali idrogenazioni. È riportata la sintesi di una serie di nuovi complessi di rutenio tridentate recanti il N -triphos ligando N (CH 2 PPh 2) 3. Inoltre, la reazione stechiometrica di un complesso diidruro RU N -triphos con acido levulinico è descritto.

La sintesi, caratterizzazione e reattività di una serie di rutenio<em&gt; N</em&gt; -triphos<sup&gt; Ph</sup&gt; Complessi

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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JoVE Journal

Chemistry

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

12.1K Views.  Imperial College London.  Complessi di Rutenio fosfina sono ampiamente utilizzati per le reazioni catalitiche omogenee quali idrogenazioni. È riportata la sintesi di una serie di nuovi complessi di rutenio tridentate recanti il N -triphos ligando N (CH 2 PPh 2) 3. Inoltre, la reazione stechiometrica di un complesso diidruro RU N -triphos con acido levulinico è descritto. 

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

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent reactions with azides to form cyanocarbene intermediates. The synthesis of hypervalent iodonium alkynyl triflates can be facile, but difficulties stem from their isolation and reactivity. In particular, the necessity to use filtration under inert atmosphere at -45 &deg;C for some HIATs requires special care and equipment. Once isolated, the compounds can be stored and used in reactions with azides to form cyanocarbene intermediates. 
The evidence for cyanocarbene generation is shown by visible extrusion of dinitrogen as well as the characterization of products that occur from O-H insertion, sulfoxide complexation, and cyclopropanation. A side reaction of the cyanocarbene formation is the generation of a vinylidene-carbene and the conditions to control this process are discussed. There is also potential to form a hypervalent iodonium alkenyl triflate and the means of isolation and control of its generation are provided. The O-H insertion reaction involves using a HIAT, sodium azide or tetrabutylammonium azide, and methanol as solvent/substrate. The sulfoxide complexation reaction uses a HIAT, sodium azide or tetrabutylammonium azide, and dimethyl sulfoxide as solvent. The cyclopropanations can be performed with or without the use of solvent. The azide source must be tetrabutylammonium azide and the substrate shown is styrene.

Herein is described the synthesis, isolation, and reactions of hypervalent iodonium alkynyl triflates (HIATs) with azides to generate cyanocarbenes. The procedures will involve air-sensitive and cryogen techniques, including cold filtration under an inert atmosphere. Handling and safety of the synthesized compounds will also be discussed.

Sintesi di hypervalent iodonio Alchinile triflati per l&#39;applicazione di Generazione Cyanocarbenes

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent ...

Ricerca

Chimica

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.

Ammide Accoppiamento di reazione per la sintesi di leganti a base di Bispyridine e il loro Complessazione di platino come diciclici agenti antitumorali

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.

Sintesi di una serie complessa Metal-Organic solubile in acqua

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.

Palladio<em&gt; N</em&gt; Complessi di Carbene eterocicliche: Sintesi dei sali di benzimidazolium e attività catalitica in reazioni di formazione di legame di carbonio-carbonio

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.

Sintesi e valutazione di un inibitore di assorbimento di calcio mitocondriale a base di rutenio

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.

Preparazione di N-(2-alkoxyvinyl) sulfamidici da N- tosyl-1, 2,3-triazoli e successiva conversione di Phthalans sostituito e fenetilamine

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.

Un<em&gt; In Vitro</em&gt; Enzimatica Assay misurare Trascrizione inibizione da gallio (III) e H<sub&gt; 3</sub&gt; 5,10,15-tris (pentafluorofenil) corroles

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

Bioingegneria

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.

Rimozione eterogenei di rutenio solubile in acqua dell'olefina metatesi catalizzatore da mezzi acquosi tramite interazione Host-Guest

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.

Photogeneration di carbeni N-eterociclico: applicazione a polimerizzazione per metatesi anello-apertura fotoindotti

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.

ARL Spectral Fitting come applicazione per aumentare i dati spettrali tramite l'analisi lineshape di Franck-Condon e l'analisi del colore

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

La sintesi, caratterizzazione e reattività di una serie di rutenio

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Sintesi di hypervalent iodonio Alchinile triflati per l'applicazione di Generazione Cyanocarbenes