The authors thank the Natural Sciences and Engineering Research Council (NSERC) of Canada and the Canada Foundation for Innovation (CFI) for funding and scholarship support.

NOTA: Solventi deuterati sono stati essiccati in base alla procedura di letteratura quando necessario, e di tutti gli altri solventi sono stati essiccati su una serie di colonne Grubbs&#39; di tipo 12 e degasate prima dell&#39;uso. Potassio 1,2,4-tris (diphenylphosphino) ciclopentadiene [K] [(Ph 2 P) 3 C 5 H 2] e la N-eterociclico carbene 1,3,4,5-tetramethylimidazole-2-ilidene (Me Me NHC ) sono stati sintetizzati secondo le procedure letteratura e quest&#39;ultima è stata sublimata prima dell&#39;uso. 9,13 Cyclohexene viene anidrificata su CaH 2, distillata e degassata prima dell&#39;uso. Acetonitrile-d 3 (CD 3 CN) e diclorometano-d 2 (CD 2 Cl 2) sono stati essiccato su pentossido di fosforo e degassata prima dell&#39;uso. La terra di diatomee è stato essiccato in stufa a 150 ° C durante la notte prima dell&#39;uso. Tutti gli altri reagenti sono stati utilizzati come ricevuti. 1. Sintesi di [dppeP] [Br] <ol><li> Dissolve 1,00 g di 1,2-bis (difenilfosfino) etano (dppe) in circa 40 ml di anidra, degassata diclorometano (DCM) in un pallone da 250 ml Schlenk, sotto gas inerte, dotato di un setto di gomma. </li><li> Con siringa o cannula, aggiungere 2,53 ml di secca, degasato, cicloesene al pallone Schlenk contenente la soluzione di agitazione dppe. </li><li> A questa soluzione, aggiungere 0,26 ml di PBr 3 tramite siringa, goccia a goccia con agitazione vigorosa. La soluzione dovrebbe diventare immediatamente precipitato giallo, pallido e bianco dopo agitazione la soluzione per 20 minuti. Lasciare che la reazione a mescolare per diverse ore o durante la notte. </li><li> Dopo agitazione per alcune ore o durante la notte, filtrata la miscela di reazione attraverso un pallone sinterizzato sormontato da una presa di terra di diatomee spessore di un pollice per rimuovere il precipitato. </li><li> Raccogliere la soluzione risultante e rimuovere il DCM sotto vuoto su una linea Schlenk. </li><li> Per l&#39;olio risultante, aggiungere circa 75 ml di tetraidrofurano (THF), mentre stirring vigorosamente (o sonicazione) per precipitare il prodotto come solido bianco. </li><li> Subito dopo le forma un precipitato bianco, la raccolta tramite filtrazione con un pallone sinterizzato in atmosfera inerte. Raccogliere il solido immediatamente, e non lasciare la sospensione a mescolare per più di 30 min. </li><li> Una volta raccolte, sciogliere una piccola quantità di [dppeP] [Br] nel CD 2 Cl 2 o CDCl 3 per ottenere 31 P, 1 H e 13 C NMR per confermare la purezza. [dppeP] [Br] possono essere conservati a tempo indeterminato in atmosfera inerte, o per diverse settimane sul banco. 6 </li></ol> 2. Sintesi di [dppeP] [IPB 4] <ol><li> Sciogliere 0,5 g di [dppeP] sale [Br] in 5 ml di DCM, in un pallone Schlenk. Agitare la soluzione sotto azoto. Quindi, aggiungere 0,35 g di tetrafenilborato di sodio in 5 ml di THF. </li><li> Lasciare che la soluzione a mescolare per diverse ore o durante la notte, fino a quando una multa forma un precipitato. </li><li> Centrifugare le suspension per eliminare il precipitato (KBr) e rimuovere il solvente a pressione ridotta per dare [dppeP] [BPH 4] come una polvere bianca. </li></ol> 3. Sintesi di [Me NHC Me 2 P] [IPB 4] <ol><li> Caricare un pallone da 100 ml Schlenk con 0,200 g di Me NHC Io e un ancoretta in atmosfera inerte. </li><li> Caricare un pallone a fondo rotondo da 100 ml con 0.603 g di [dppeP] [4 IPB] in atmosfera inerte. </li><li> Cannula 20 ml di THF al pallone Schlenk contenente 0,200 g di Me Me NHC e iniziare agitazione magnetica. </li><li> Cannula 20 ml di THF ai 100 ml pallone a fondo tondo con 0,603 g di [dppeP] [4 IPB] e mescolare fino a scioglimento. </li><li> Cannula trasferire la soluzione di [dppeP] [IPB 4] in THF alla soluzione agitazione di Me Me NHC in THF e consentire la soluzione gialla a mescolare per 1 ora. </li><li> Concentrare le s gialloolution ad un terzo del volume originale (13 ml) sotto pressione ridotta. </li><li> Aggiungere dietiletere (Et 2 O) (40 ml) alla soluzione concentrata agitazione per avviare precipitazione del prodotto giallo e consentire la sospensione risultante a mescolare per 20 min. </li><li> Inserire una fritta sigillato montato collegato a un pallone da 100 ml Schlenk sulla linea Schlenk e creare un&#39;atmosfera inerte evacuando la beuta usando il vuoto e riempire il matraccio con azoto dalla linea Schleck. Evacuare per 5 minuti e riempire con azoto per 3 volte per assicurare un&#39;atmosfera inerte. </li><li> Cannula trasferire la sospensione Et 2 O nell&#39;apparecchio e filtrare il precipitato. </li><li> Lavare il precipitato con 10 ml di Et 2 O tre volte e lasciare il precipitato asciugare sotto pressione ridotta per 2 ore. </li><li> Opzionali) permettono il filtrato e lavaggi ad evaporare lentamente sotto azoto per ricristallizzare PDPE. Lavare i cristalli con una minima quantità di esano, secca, e raccogliere ilcristalli per il riutilizzo. </li></ol> 4. Sintesi di (Ph 2 P) C 5 H 2 (Ph 2 P) 2 P <ol><li> Per un 150 ml pallone Schlenk contenente 0.484g [dppeP] [Br] in atmosfera inerte, aggiungere 40 ml di secca, degassato THF. </li><li> Posizionare il Schlenk in un bagno di ghiaccio secco / acetone per raffreddare la sospensione a -78 ° C. </li><li> Cannula trasferire una soluzione THF di 0.625g [K] [(Ph 2 P) 3 C 5 H 2] in un pallone a fondo tondo, al flash Schlenk contenente [dppeP] [Br]. </li><li> Quando l&#39;aggiunta è completa, rimuovere il pallone Schlenk dal bagno di acetone e lasciarla riscaldare a temperatura ambiente. Dopo agitazione per 2 ore, la soluzione sarà giallo chiaro con un precipitato bianco presente. </li><li> Trasferire la sospensione in un filtro poroso privo di aria dotato di un pallone da 150 ml Schlenk, per rimuovere il precipitato bianco (KBr). </li><li> Raccogliere la soluzione gialla e rimuovere il THF sotto vuoto. </li><li> Aggiungere un 80:20miscela di secco e degasato dietiletere: pentano l&#39;olio risultante e lasciare agitare per 20 min. </li><li> Raccogliere il prodotto (Ph 2 P) C 5 H 2 (Ph 2 P) 2 P come un precipitato giallo pallido filtrando la sospensione attraverso una, pallone sinterizzato privo di aria. La soluzione rimanente etere / pentano contiene l&#39;impurità dppe e può essere scartata o il solvente può essere rimosso sotto vuoto ed il dppe raccolti per ulteriore uso. </li></ol>

<ol><li>Macdonald, C. L. B., Ellis, B. D., Swidan, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Low-Oxidation-State+Main+Group+Compounds%5BTitle%5D)+AND+%22Encyclopedia+of+Inorganic+and+Bioinorganic+Chemistry%22%5BJournal%5D)">Low-Oxidation-State Main Group Compounds.</a> Encyclopedia of Inorganic and Bioinorganic Chemistry. , (2011).</li>
<li>Coffer (née Monks), P. K., Dillon, K. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Cyclic+triphosphenium+ions+and+related+species%5BTitle%5D)+AND+%22Coord.+Chem.+Rev%22%5BJournal%5D)">Cyclic triphosphenium ions and related species.</a> Coord. Chem. Rev. 257 (5-6), 910-923 (2013).</li>
<li>Schmidpeter, A., Lochschmidt, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((New+Products+from+PCl3%2C+P%28NMe2%293%2C+and+AlCl3%5BTitle%5D)+AND+%22Angew.+Chem.+Internat.+Ed.+in+Engl%22%5BJournal%5D)">New Products from PCl3, P(NMe2)3, and AlCl3.</a> Angew. Chem. Internat. Ed. in Engl. 25 (3), 253-254 (1986).</li>
<li>Schmidpeter, A., Lochschmidt, S., Karaghiosoff, K., Sheldrickb, W. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Triphosphane-l%2C3-di-ium+Ions%5BTitle%5D)+AND+%22J.+Chem.+Soc.+Chem.+Commun%22%5BJournal%5D)">Triphosphane-l,3-di-ium Ions.</a> J. Chem. Soc. Chem. Commun. , 1447-1448 (1985).</li>
<li>Ellis, B. D., Carlesimo, M., Macdonald, C. L. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Stabilised+phosphorus%28I%29+and+arsenic%28I%29+iodide%3A+readily-synthesised+reagents+for+low+oxidation+state+main+group+chemistry%5BTitle%5D)+AND+%22Chem.+Commun%22%5BJournal%5D)">Stabilised phosphorus(I) and arsenic(I) iodide: readily-synthesised reagents for low oxidation state main group chemistry.</a> Chem. Commun. 15 (15), 1946-1947 (2003).</li>
<li>Norton, E. L., Szekely, K. L. S., Dube, J. W., Bomben, P. G., Macdonald, C. L. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((A+convenient+preparative+method+for+cyclic+triphosphenium+bromide+and+chloride+salts%5BTitle%5D)+AND+%22Inorg.+Chem%22%5BJournal%5D)">A convenient preparative method for cyclic triphosphenium bromide and chloride salts.</a> Inorg. Chem. 47 (3), 1196-1203 (2008).</li>
<li>Ellis, B. D., Macdonald, C. L. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Phosphorus%28I%29+iodide%3A+a+versatile+metathesis+reagent+for+the+synthesis+of+low+oxidation+state+phosphorus+compounds%5BTitle%5D)+AND+%22Inorg.+Chem%22%5BJournal%5D)">Phosphorus(I) iodide: a versatile metathesis reagent for the synthesis of low oxidation state phosphorus compounds.</a> Inorg. Chem. 45 (17), 6864-6874 (2006).</li>
<li>Kosnik, S. C., Farrar, G. J., Norton, E. L., Cooper, B. F. T., Ellis, B. D., Macdonald, C. L. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Low-Valent+Chemistry%3A+An+Alternative+Approach+to+Phosphorus-+Containing+Oligomers%5BTitle%5D)+AND+%22Inorg.+Chem%22%5BJournal%5D)">Low-Valent Chemistry: An Alternative Approach to Phosphorus- Containing Oligomers.</a> Inorg. Chem. 11 (53), 13061-13069 (2014).</li>
<li>Kosnik, S. C., Macdonald, C. L. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((A+zwitterionic+triphosphenium+compound+as+a+tunable+multifunctional+donor%5BTitle%5D)+AND+%22Dalton+Trans%22%5BJournal%5D)">A zwitterionic triphosphenium compound as a tunable multifunctional donor.</a> Dalton Trans. 45 (14), 6251-6258 (2016).</li>
<li>Binder, J. F., Swidan, A., Tang, M., Nguyen, J. H., Macdonald, C. L. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Remarkably+stable+chelating+bis-N-heterocyclic+carbene+adducts+of+phosphorus%28I%29+cations%5BTitle%5D)+AND+%22Chem.+Commun%22%5BJournal%5D)">Remarkably stable chelating bis-N-heterocyclic carbene adducts of phosphorus(I) cations.</a> Chem. Commun. 51 (36), 7741-7744 (2015).</li>
<li>Binder, J. F., Corrente, A. M., Macdonald, C. L. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((A+simple+route+to+phosphamethine+cyanines+from+S%2CN-heterocyclic+carbenes%5BTitle%5D)+AND+%22Dalton+Trans%22%5BJournal%5D)">A simple route to phosphamethine cyanines from S,N-heterocyclic carbenes.</a> Dalton Trans. 45 (5), 2138-2147 (2016).</li>
<li>Pangborn, A. B., Ma Giardello,, Grubbs, R. H., Rosen, R. K., Timmers, F. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Safe+and+Convenient+Procedure+for+Solvent+Purification%5BTitle%5D)+AND+%22Organometallics%22%5BJournal%5D)">Safe and Convenient Procedure for Solvent Purification.</a> Organometallics. 15 (5), 1518-1520 (1996).</li>
<li>Smaliy, R. V., Beaupérin, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Hexaphosphine%3A+A+multifaceted+ligand+for+transition+metal+coordination%5BTitle%5D)+AND+%22Eur.+J.+Inorg.+Chem%22%5BJournal%5D)">Hexaphosphine: A multifaceted ligand for transition metal coordination.</a> Eur. J. Inorg. Chem. (9), 1347-1352 (2012).</li>
<li>Klebach, T. C., Lourens, R., Bickelhaupt, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Synthesis+of+mesityldiphenylmethylenephosphine%3A+a+stable+compound+with+a+localized+phosphorus%3Acarbon+bond%5BTitle%5D)+AND+%22J.+Amer.+Chem.+Soc%22%5BJournal%5D)">Synthesis of mesityldiphenylmethylenephosphine: a stable compound with a localized phosphorus:carbon bond.</a> J. Amer. Chem. Soc. 100 (15), 4886-4888 (1978).</li>
<li>Alcarazo, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((%CE%B1-Cationic+Phosphines%3A+Synthesis+and+Applications%5BTitle%5D)+AND+%22Chem.+Eur.+J%22%5BJournal%5D)">α-Cationic Phosphines: Synthesis and Applications.</a> Chem. Eur. J. 20 (26), 7868-7877 (2014).</li>
</ol>

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Strutture cristalline e NMR multi-nucleare (31 P, 1 H e 13 C) sono stati ottenuti per tutti i prodotti segnalati per confermare la connettività. Elettrospray ionizzazione spettrometria di massa è stata utilizzata per confermare la presenza di cationi e analisi elementare è stata utilizzata per confermare la purezza specifica dei campioni. E &#39;indispensabile che tutte le reazioni sono fatte in un ambiente asciutto e privo di aria per garantire che nessun...

La chimica degli elementi dei gruppi principali in insolitamente bassi di ossidazione o di valenza Uniti è stata una zona di notevole interesse nel corso degli ultimi due decenni. 1 A parte l&#39;interesse fondamentale derivante dal loro legame e la struttura unica, tali composti spesso mostrano reattività che sono molto diversi da quelli delle loro controparti più tipici stato di ossidazione. In questo senso, essi offrono un potenziale significativo come reagenti per la costruzione di altri principali gruppi elementi contenente materiali complessi. Una classe punto di riferimento di basso-valente fosforo contenenti molecole sono cationi &quot;triphosphenium&quot; che sono stati segnalati dai Schmidpeter nel 1980. 2 Questi ioni dispongono di un dicoordinate di fosforo (I) agli ioni di legatura da due sostituenti phosphonio, con le varianti più stabili costruiti da un . chelante quadro 3,4 il nostro gruppo ha ottimizzato le sintesi di sali di alogenuro triphosphenium 5-7 e hahanno dimostrato che questi composti stabili sono versatili trasferitori P + che sono utili per la sintesi controllata di fosforo (I) oligomeri -aventi, 8 zwitterione, 9 e coloranti cianinici phosphamethine. 10,11 Mentre le sintesi originali di tali composti comprendono spesso fosforo pericolose -contenente reagenti e / o altamente condizioni riducenti, il percorso controllato presentiamo è sicuro, P-atomo efficiente e conveniente. I risultati del metodo di materiali di alta purezza, che possono essere utilizzati come coloranti, leganti per complessi di metalli di transizione e precursori per più specie contenenti fosforo complesse.

<table><tbody><tr><td>bis(diphenyl)phosphino ethane (dppe)</td><td>Strem</td><td>1663-45-2</td><td>98% Stored in gloved box, used as is.&amp;nbsp;</td></tr><tr><td>Anhydrous Dichloromethane (DCM)</td><td>Sigma Aldrich</td><td>270997</td><td>Purified through solvent purification system, or standard methods</td></tr><tr><td>Anhydrous Cyclohexene</td><td>Sigma Aldrich</td><td>29240</td><td>Dried over calcium hydride and distilled.</td></tr><tr><td>Phosphorus Tribromide (PBr&lt;sub&gt;3&lt;/sub&gt;)</td><td>Sigma Aldrich</td><td>157783</td><td>99% Stored in glove box, used as is. Air sensitive.</td></tr><tr><td>Anyhydrous Tetrahydrofuran (THF)</td><td>Sigma Aldrich</td><td>401757</td><td>Purified through solvent purification system, or standard methods</td></tr><tr><td>Methylene Chloride-D&lt;sub&gt;2&lt;/sub&gt; (CD&lt;sub&gt;2&lt;/sub&gt;Cl&lt;sub&gt;2&lt;/sub&gt;)</td><td>Sigma Aldrich</td><td>DLM-23-25</td><td>Dried over phosphorus pentoxide, vacuum transferred or distilled</td></tr><tr><td>Acetonitrile</td><td>Alfa Aesar</td><td>5/8/1975</td><td>Stored in glove box, used as is</td></tr><tr><td>Sodium Tetraphenylborate</td><td>Sigma Aldrich</td><td>T25402</td><td>Stored in glove box, used as is</td></tr><tr><td>Anyhydrous Diethyl Ether&amp;nbsp;</td><td>Sigma Aldrich</td><td>673811</td><td>Purified through solvent purification system, or standard methods</td></tr><tr><td>Anhydrous Pentane</td><td>Sigma Aldrich</td><td>236705</td><td>Purified through solvent purification system, or standard methods</td></tr></tbody></table>

preparation and reactivity of a triphosphenium bromide salt: a convenient and stable source of phosphorus(i)

Presentiamo qui la sintesi ottimizzata di un sale triphosphenium bromuro. Oltre ad essere un reagente di metatesi versatile, questo composto low-valente-contenente fosforo insolitamente stabile agisce come un utile agente di trasferimento P +. A differenza dei metodi tradizionali impiegati per accedere a bassa coordinate specie fosforo che di solito richiedono precursori piroforiche contenenti fosforo (fosforo bianco, Tris (trimetilsilil) fosfina, ecc), o agenti riducenti aggressivi (metalli alcalini, grafite potassio, ecc), la corrente approccio non comporta reagenti piroforici o esplosivi e può essere fatto su larga scala (&gt; 20 g) in ottime rese da studenti universitari con una formazione sintetico privo di aria di base. Lo ione contatore bromuro è facilmente scambiato con altri anioni quali tetrafenil borato (qui descritto) utilizzando reagenti tipici sale metatesi di ottenere materiali con proprietà e reattività desiderate. La versatilità di questo P + trasferimento diPPROCCIO è esemplificata dalle reazioni di questi precursori triphosphenium con un carbene N-eterociclico e un bisphosphine anionico, ciascuna delle quali facilmente spostare il bisphosphine neutro per dare un fosforo (I) catione NHC stabilizzato e fosforo (I) contenente zwitterion rispettivamente .

Un sale stabile ([dppeP] [Br]) contenente una sorgente a bassa valente fosforo (I) può essere sintetizzato facilmente con l&#39;aggiunta di PBr 3 a diphenylphosphinoethane (dppe) in presenza di un eccesso di cicloesene (Figura 1) 6. Al lavoro della reazione, 31 spettri P NMR mostrano la presenza di un segnale tripletta che è significativamente schermato a -220 ppm, e un segnale doppietto a 50 ppm. Forte acco...

Watch this Scientific Journal Video about Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI at JoVE.com

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

The synthesis of a triphosphenium bromide salt is described and its use as a P+ transfer agent is outlined by reactions with an N-heterocyclic carbene and an anionic bisphosphine, yielding an NHC-stabilized P(I) cation and a P(I) containing zwitterion, respectively.

Preparazione e reattività di un Triphosphenium Bromuro di sale: una fonte conveniente e stabile di fosforo (I)

We present herein the optimized synthesis of a triphosphenium bromide salt. Apart from being a versatile metathesis reagent, this unusually stable ...

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Chemistry

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)

7.7K Views.  University of Windsor. The synthesis of a triphosphenium bromide salt is described and its use as a P+ transfer agent is outlined by reactions with an N-heterocyclic carbene and an anionic bisphosphine, yielding an NHC-stabilized P(I) cation and a P(I) containing zwitterion, respectively.

Video: Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

Nucleoside Triphosphates - From Synthesis to Biochemical Characterization

The traditional strategy for the introduction of chemical functionalities is the use of solid-phase synthesis by appending suitably modified phosphoramidite precursors to the nascent chain. However, the conditions used during the synthesis and the restriction to rather short sequences hamper the applicability of this methodology. On the other hand, modified nucleoside triphosphates are activated building blocks that have been employed for the mild introduction of numerous functional groups into nucleic acids, a strategy that paves the way for the use of modified nucleic acids in a wide-ranging palette of practical applications such as functional tagging and generation of ribozymes and DNAzymes. One of the major challenges resides in the intricacy of the methodology leading to the isolation and characterization of these nucleoside analogues.
	
	In this video article, we present a detailed protocol for the synthesis of these modified analogues using phosphorous(III)-based reagents. In addition, the procedure for their biochemical characterization is divulged, with a special emphasis on primer extension reactions and TdT tailing polymerization. This detailed protocol will be of use for the crafting of modified dNTPs and their further use in chemical biology.

The protocol described herein aims to explain and abridge the numerous obstacles in the way of the intricate route leading to modified nucleoside triphosphates. Consequently, this protocol facilitates both the synthesis of these activated building-blocks and their availability for practical applications.

Nucleosidi trifosfati - Dalla sintesi di biochimica Caratterizzazione

The  traditional strategy for the introduction of chemical functionalities is the  use of solid-phase synthesis by appending suitably modified ...

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Chimica

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

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

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

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

Mizoroki-Heck reazioni di cross-coupling catalizzate da dicloro {bis [1,1 &#39;, 1&#39;&#39; - (phosphinetriyl) tripiperidine]} palladio Sotto lievi condizioni di reazione

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 ...

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures in multi-gram scale quantities. The goal of this manuscript is to clearly detail how to handle and prepare these unique carbenes such that a synthetic chemist of any skill level can work with them. The two carbenes described are a diamidocarbene (DAC, carbene 1) and a monoamidoaminocarbene (MAAC 2). These carbenes are highly electron-deficient and as such display reactivity profiles that are atypical of more traditional N-heterocyclic carbenes. Additionally, these two carbenes only differ in their electrophilic character and not their steric parameters, making them ideal for studying how carbene electronics influence reactivity. To demonstrate this phenomenon, we are also describing the activation of white phosphorus (P4) using these carbenes. Depending on the carbene used, two very different phosphorus-containing compounds can be isolated. When the DAC 1 is used, a tris(phosphaalkenyl)phosphane can be isolated as the exclusive product. Remarkably however, when MAAC 2 is added to P4 under identical reaction conditions, an unexpected carbene-supported P8&#160;allotrope of phosphorus is isolated exclusively. Mechanistic studies demonstrate that this carbene-supported P8allotrope forms via a [2+2] cycloaddition dimerization of a transient diphosphene which has been trapped by treatment with 2,3-dimethyl-1,3-butadiene.

Here, we present a protocol for the synthesis of two carbonyl-decorated carbenes. The protocol makes these interesting compounds readily available to chemists of all skill levels. In addition to the synthesis of these two carbenes, their use in the activation of white phosphorus is also described.

Preparazione e utilizzo di carbeni carbonile-decorate in Attivazione di fosforo bianco

Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures ...

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

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-&#954;3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-&#954;3P{CH3CO(CH2)2CO2H}-&#954;2O](PF6) (6).

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

Ruthenium phosphine complexes are widely used for homogeneous catalytic reactions such as hydrogenations. The synthesis of a series of novel tridentate ruthenium complexes bearing the N-triphos ligand N(CH2PPh2)3 is reported. Additionally, the stoichiometric reaction of a dihydride Ru&#8211;N-triphos complex with levulinic acid is described.

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 ...

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica glass ampules). Reduction of such phases by elemental alkaline metals in amines affords crystalline chalcogenidoplumbate(II) salts comprised of [PbTe3]2- or [Pb2Ch3]2- anions, depending upon which sequestering agent for the cations is present: crown ethers, like 18-crown-6, or cryptands, like [2.2.2]crypt. Reactions of solutions of such anions with transition-metal compounds yield (poly-)chalcogenide anions or transition-metal chalcogenide clusters, including one with a &#181;-PbSe ligand (i.e., the heaviest-known CO homolog).
In contrast, the solid-state synthesis of a phase of the nominal composition &#34;K2PbSe2&#34; by successive reactions of the elements and by the subsequent solvothermal treatment in amines yields the first non-oxide/halide inorganic lead(IV) compound: a salt of the ortho-selenidoplumbate(IV) anion [PbSe4]4-. This was unexpected due to the redox potentials of Pb(IV) and Se(-II). Such methods can further be applied to other elemental combinations, leading to the formation of solutions with binary [HgTe2]2- or [BiSe3]3- anions, or to large-scale syntheses of K2Hg2Se3 or K3BiSe3 via the solid-state route.
All compounds are characterized by single-crystal X-ray diffraction and elemental analysis; solutions of plumbate salts can be investigated by 205Pb and 77Se or 127Te NMR techniques. Quantum chemical calculations using density functional theory methods enable energy comparisons. They further allow for insights into the electronic configuration and thus, the bonding situation. Molecular Rh-containing Chevrel-type compounds were found to exhibit delocalized mixed valence, whereas similar telluridopalladate anions are electron-precise; the cluster with the &#181;-PbSe ligand is energetically favored over a hypothetical CO analog, in line with the unsuccessful attempt at its synthesis. The stability of formal Pb(IV) within the [PbSe4]4- anion is mainly due to a suitable stabilization within the crystal lattice.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

La combinazione a stato solido e tecniche di soluzione a base di: Sintesi e reattività di Chalcogenidoplumbates (II o IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica ...

Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants

We present the synthesis of (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example to demonstrate a method for the synthesis of high purity nonsymmetric dialkylphosphinic acid extractants. Low toxic sodium hypophosphite was chosen as the phosphorus source to react with olefin A (2,3-dimethyl-1-butene) to generate a monoalkylphosphinic acid intermediate. Amantadine was adopted to remove the dialkylphosphinic acid byproduct, as only the monoalkylphosphinic acid can react with amantadine to form an amantadine&#8729;mono-alkylphosphinic acid salt, while the dialkylphosphinic acid cannot react with amantadine due to its large steric hindrance. The purified monoalkylphosphinic acid was then reacted with olefin B (diisobutylene) to yield nonsymmetric dialkylphosphinic acid (NSDAPA). The unreacted monoalkylphosphinic acid can be easily removed by a simple base-acid post-treatment and other organic impurities can be separated out through the precipitation of the cobalt salt. The structure of the (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid was confirmed by 31P NMR, 1H NMR, ESI-MS, and FT-IR. The purity was determined by a potentiometric titration method, and the results indicate that the purity can exceed 96%.

A protocol for the synthesis of high purity nonsymmetric dialkylphosphinic acid extractants is presented, taking (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example.

Sintesi di elevata purezza il Dialkylphosphinic acido solventi

We present the synthesis of (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example to demonstrate a method for the synthesis of high ...

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 ...

Sintesi di MOF a basso valenza da linker fosfinici multitopici

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown to be a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from those in the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on the following: 1) the judicious choice of the metal precursor, modulator, and solvent; 2) the experimental procedures, air-free techniques, and required equipment; 3) the proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier to this new subfield of MOF research and facilitate advancements toward novel catalytic materials.

Autore in primo piano: Approcci sperimentali per la sintesi di strutture metallo-organiche a bassa valenza da linker fosfinici multitopici  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous catalysts.

Approcci sperimentali per la sintesi di strutture metallo-organiche a basso contenuto di valenti da linker multitopici di fosfina

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, ...

Preparazione e reattività di un Triphosphenium Bromuro di sale: una fonte conveniente e stabile di fosforo (I)

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Preparazione e utilizzo di carbeni carbonile-decorate in Attivazione di fosforo bianco

La sintesi, caratterizzazione e reattività di una serie di rutenio

La combinazione a stato solido e tecniche di soluzione a base di: Sintesi e reattività di Chalcogenidoplumbates (II o IV)

Sintesi di elevata purezza il Dialkylphosphinic acido solventi

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

Approcci sperimentali per la sintesi di strutture metallo-organiche a basso contenuto di valenti da linker multitopici di fosfina

Approcci sperimentali per la sintesi di strutture metallo-organiche a basso contenuto di valenti da linker multitopici di fosfina

Approcci sperimentali per la sintesi di strutture metallo-organiche a basso contenuto di valenti da linker multitopici di fosfina