Name: preparation and reactivity of a triphosphenium bromide salt: a convenient and stable source of phosphorus(i)
Uploaded: 2016-11-22T15:00:00.000+00:00
Duration: 8 min 46 s
Description: Watch this Scientific Journal Video about Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI at JoVE.com

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: solventes deuterados foram secos de acordo com o procedimento da literatura quando necessário, e todos os outros solventes foram secas sobre uma série de colunas Grubbs&#39;-tipo 12 e desgaseificada antes do uso. Potássio 1,2,4-tris (dif enilf osf ino) ciclopentadieno [K] [(Ph 2 P) 3 C 5 H 2] e N-heterocíclico de carbeno 1,3,4,5-tetramethylimidazole-2-ilideno (Me Me NHC ) foram sintetizados de acordo com procedimentos da literatura e esta última foi sublimado antes de ser utilizado. 9,13 ciclohexeno foi seca sobre CaH 2, destilada e desgaseificada antes do uso. Acetonitrilo-d 3 (CD 3 CN) e diclorometano-d 2 (CD 2 Cl 2) foram secos sobre pentóxido de fósforo e desgaseificada antes do uso. A terra de diatomáceas foi seco num forno a 150 ° C durante a noite antes da utilização. Todos os outros reagentes foram utilizados como recebidos. 1. Síntese de [dppeP] [Br] <ol><li> Dissolve 1,00 g de 1,2-bis (difenilfosfino) etano (dppe) em cerca de 40 ml de anidro, desgaseificado diclorometano (DCM) em um balão de Schlenk de 250 ml, sob atmosfera de gás inerte, equipado com um septo de borracha. </li><li> Por meio de seringa ou cânula de transferência, adicionar 2,53 ml de seco, desgaseif içado, ciclo-hexeno para o balão de Schlenk contendo a solução em agitação de DPPE. </li><li> A esta solução, adicionar 0,26 mL de PBr3 através de uma seringa, gota a gota com agitação vigorosa. A solução deve transformar imediatamente formas precipitado amarelo e branco pálido após agitação da solução durante 20 min. Deixar a reacção a agitar durante várias horas ou durante a noite. </li><li> Depois de se agitar durante várias horas ou durante a noite, filtrar a mistura reaccional através de um balão de vidro poroso coberto com uma espessa tampão de terra de diatomáceas de uma polegada para remover o precipitado. </li><li> Recolher a solução resultante e remover o DCM sob vácuo numa linha de Schlenk. </li><li> Ao óleo resultante, adicionar cerca de 75 ml de tetra-hidrofurano (THF), enquanto rirring vigorosamente (ou sonicação) para precipitar o produto como um sólido branco. </li><li> Imediatamente após a formar um precipitado branco, recolhê-lo através de filtração com um frasco de vidro sinterizado, sob uma atmosfera inerte. Recolhe-se o sólido imediatamente, e não deixar a suspensão a agitar durante mais de 30 min. </li><li> Uma vez recolhidos, dissolve-se uma pequena quantidade de [dppeP] [Br] no CD 2 Cl 2 ou CDCl3 obter 31 P, 1 H e 13 C RMN para confirmar a pureza. [dppeP] [Br] pode ser armazenado indefinidamente sob uma atmosfera inerte, ou durante várias semanas na bancada. 6 </li></ol> 2. Síntese de [dppeP] [BPh 4] <ol><li> Dissolve-se 0,5 g de [dppeP] sal [Br] em 5 ml de DCM, num balão de Schlenk. Agita-se a solução sob atmosfera de azoto. Em seguida, adicionar 0,35 g de tetrafenilborato de sódio em 5 ml de THF. </li><li> Permitir que a solução a agitar durante várias horas ou durante a noite, até se formar um precipitado fino. </li><li> Centrifugar os sUSPENSÃO para eliminar o precipitado (KBr) e remover o solvente sob pressão reduzida para se obter o ácido [dppeP] [BPh 4] como um pó branco. </li></ol> 3. Síntese de [Me NHC Me 2 P] [BPh 4] <ol><li> Carregar um frasco de 100 ml Schlenk com 0,200 g de Mim NHC Me e uma barra de agitação sob uma atmosfera inerte. </li><li> Carregar um frasco de 100 ml de fundo redondo, com 0,603 g de [dppeP] [4 BPh] sob uma atmosfera inerte. </li><li> Cânula de transferência de 20 mL de THF ao balão de Schlenk contendo 0,200 g de Me NHC Me e começar agitação magnética. </li><li> Transferência de cânula 20 ml de THF para balão de 100 ml de fundo redondo com 0,603 g de [dppeP] [4 BPh] e agita-se até se dissolver. </li><li> Cânula transferir a solução de [dppeP] [BPh 4] em THF à solução em agitação de Me Me NHC em THF e permitir que a solução de cor amarela a agitar durante 1 h. </li><li> Concentrar as s amarelaslução a um terço do volume original (13 ml) sob pressão reduzida. </li><li> Adicionar éter dietílico (Et2O) (40 ml) à solução concentrada agitação para iniciar a precipitação do produto amarelo e permitir que a suspensão resultante a agitar durante 20 min. </li><li> Coloque uma frita selado equipado ligado a um balão de Schlenk de 100 ml na linha de Schlenk e criar uma atmosfera inerte, por evacuação do frasco usando vácuo e enchimento do balão com azoto a partir da linha Schleck. Evacuar durante 5 minutos e volte a encher com azoto 3 vezes para garantir uma atmosfera inerte. </li><li> Cânula transferir a suspensão Et2O para dentro do aparelho e filtrar o precipitado. </li><li> Lavar o precipitado com 10 mL de Et2O três vezes e permitir que o precipitado a secar sob pressão reduzida durante 2 horas. </li><li> Opcional) Permitir que o filtrado e as lavagens para se evaporar lentamente, sob azoto, para recristalizar DPPE. Lavar os cristais com uma quantidade mínima de hexano, seco, e recolher ocristais para reutilização. </li></ol> 4. Síntese de (Ph 2 P) C 5 H 2 (Ph 2 P) 2P <ol><li> Para um balão de Schlenk de 150 ml contendo 0.484g [dppeP] [BR], numa atmosfera inerte, adicionar 40 ml de seco, desgaseificado THF. </li><li> Coloque a Schlenk em um banho de gelo seco / acetona para se arrefecer a suspensão até -78 ° C. </li><li> Cânula transferir uma solução em THF de 0,625 g [K] [(Ph 2 P) 3 C 5 H 2] num balão de fundo redondo, ao flash de Schlenk contendo [dppeP] [Br]. </li><li> Quando a adição está completa, o balão de Schlenk de remover a partir do banho de acetona e deixa-se aquecer até à temperatura ambiente. Depois de se agitar durante 2 h, a solução será amarelo claro com um precipitado branco presente. </li><li> Transferir a suspensão para um filtro de frita isenta de ar equipada com um balão de Schlenk de 150 ml, para remover o precipitado branco (KBr). </li><li> Recolher a solução amarela e remover o THF sob vácuo. </li><li> Adicionar uma mistura 80:20mistura de éter dietílico seco e desgaseificado: pentano para o óleo resultante e agita-se durante 20 min. </li><li> Recolhe-se o produto (Ph 2 P) C 5 H 2 (Ph 2 P) P 2 como um precipitado amarelo pálido por filtração da suspensão através de, um frasco de vidro sinterizado livre de ar. A solução de éter / pentano restante contém a impureza DPPE e pode ser descartado ou o solvente pode ser removido sob vácuo e o DPPE recolhido para uso posterior. </li></ol>

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	<li>Macdonald, C. L. B., Ellis, B. D., Swidan, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Low-Oxidation-State+Main+Group+Compounds.">Low-Oxidation-State Main Group Compounds.</a> Encyclopedia of Inorganic and Bioinorganic Chemistry. , (2011).</li><li>Coffer (n&#233;e Monks), P. K., Dillon, K. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cyclic+triphosphenium+ions+and+related+species.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=New+Products+from+PCl3,+P(NMe2)3,+and+AlCl3.">New Products from PCl3, P(NMe2)3, and AlCl3.</a> Angew. Chem. Internat. 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Os autores não têm nada para revelar.

Estruturas cristalinas e RMN multi-nuclear (31 P, 1 H e 13 C) foram obtidos para todos os produtos relatados para confirmar a conectividade. espectrometria de massa de electrospray de ionização foi usada para confirmar a presença dos catiões e análise elementar foi usada para confirmar a pureza analítica das amostras. É imperativo que todas as reações são realizadas em um ambiente seco e sem ar para garantir que nenhum inesperada subprodutos ou prod...

A química dos principais elementos do grupo em anormalmente baixos de oxidação ou de valência estados tem sido uma área de interesse significativo ao longo das últimas duas décadas. 1 Além do interesse fundamental decorrente da sua ligação e estrutura única, esses compostos apresentam muitas vezes reacções que são muito diferentes dos as dos seus mais típicos homólogos estado de oxidação. Neste sentido, eles oferecem um potencial significativo como reagentes para a construção de mais principais grupo de elementos que contém materiais complexos. Uma classe marco de fósforo baixo-valente contendo moléculas são cátions &quot;triphosphenium&quot; que foram relatados pela primeira vez por Schmidpeter na década de 1980. 2 Esses íons apresentam um íon dicoordinate fósforo (I) ligado por dois substituintes phosphonio, com as variantes mais estáveis construída a partir de um . quelante enquadramento 3,4 Nosso grupo tem otimizado a síntese de sais de iodetos triphosphenium 5-7 e temdemonstraram que estes compostos estáveis são agentes de transferência de P + versáteis que são úteis para a síntese controlada de fósforo (I) Os oligómeros molecular contendo, 8, 9 e zwiteriões corantes de cianina phosphamethine 10,11. Embora as sínteses originais de tais compostos de fósforo, muitas vezes envolvem perigosas molecular contendo reagentes e / ou reduzindo altamente condições, o percurso controlado apresentamos é seguro, P-átomo eficiente e conveniente. O método resulta em materiais de elevada pureza, que podem ser utilizadas como corantes, os ligandos para complexos de metais de transição e os precursores para as espécies mais complexas contendo fósforo.

<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)

Apresentamos aqui a síntese optimizada de um sal brometo de triphosphenium. Para além de ser um reagente de metátese versátil, este composto de baixo-valente-fósforo contendo invulgarmente estável actua como um agente de transferência de P + útil. Ao contrário de métodos tradicionais utilizados para acesso de baixo coordenar espécies de fósforo, que geralmente requerem pirofóricas precursores contendo fósforo (fósforo branco, tris (trimetilsilil) f osf ina, etc), ou agentes redutores agressivos (grafite, metais alcalinos potássio, etc), o actual abordagem não envolve reagentes pirofóricos ou explosivos e pode ser feito em grandes escalas (&gt; 20 g) em excelentes rendimentos por alunos de graduação com formação sintética sem ar básica. O contra-ião brometo é facilmente trocado por outros aniões, tais como borato de tetrafenilo (aqui descrito), utilizando reagentes típicos de metátese sal para se obter materiais com propriedades e reactividade desejados. A versatilidade deste P + transferência de umBORDAGEM é exemplificado pelas reacções destes precursores triphosphenium com um carbeno N-heterocíclico e uma bisfosfina aniónico, cada um dos quais deslocar facilmente a bisfosfina neutra para dar um fósforo catião NHC-estabilizado (I) e um fósforo (I) contendo ião dipolar, respectivamente .

Um sal estável ([dppeP] [Br]) contendo uma fonte (I) de baixa valência de fósforo podem ser sintetizados facilmente por meio da adição de PBr3 a diphenylphosphinoethane (DPPE) na presença de um excesso de ciclo-hexeno (Figura 1) 6. Após o processamento da reacção, 31 Os espectros de RMN P mostrar a presença de um sinal de tripleto que é significativamente blindado em -220 ppm, e um sinal de dupleto ...

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.

Preparação e Reatividade de uma Triphosphenium Brometo Sal: Uma fonte adequada e estável de fósforo (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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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)

7.7K visualizações.  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.

Vídeo: 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.

Nucleosídeos Trisfosfatos - Da síntese à Caracterização Bioquímica

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

Química

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 Reações de acoplamento cruzado catalisado por Dicloro {bis [1,1 &#39;, 1&#39;&#39; - (phosphinetriyl) tripiperidine]} paládio sob condições de reação leves

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.

Preparação e Utilização de carbenos Carbonyl decorados na ativação de fósforo branco

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.

A Síntese, Caracterização e Reatividade de uma série de Rutênio<em&gt; N</em&gt; -triphos<sup&gt; Ph</sup&gt; Complexos

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.

Combinando Solid-state e técnicas baseadas em Solução: Síntese e reatividade de Chalcogenidoplumbates (II ou 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.

Síntese de alta pureza da gravitação assimétrica Dialkylphosphinic ácido 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 ...

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.

Preparação de N-(2-alcoxivinil)sulfonamidas a partir de N-tosil-1,2,3-triazóis e Conversão Subsequente para Fitalanos e Fenetilaminas Substituídas

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

Síntese de MOFs de baixa valência a partir de ligantes de fosfina multitópicos

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.

Autor em destaque: Abordagens experimentais para a síntese de estruturas metal-orgânicas de baixa valência a partir de ligantes de fosfina multitópicos  

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.

Abordagens Experimentais para a Síntese de Estruturas Metal-Orgânicas de Baixa Valência a partir de Ligantes Multitópicos de Fosfina

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

Preparação e Reatividade de uma Triphosphenium Brometo Sal: Uma fonte adequada e estável de fósforo (I)

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