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.

주 : 중수소 용매가 필요하고, 다른 모든 용매 Grubbs&#39; 형 컬럼 (12)의 연속상에서 건조시키고 사용 전에 탈기 때 문헌 과정에 따라 건조시켰다. 칼륨 1,2,4- 트리스 (디 페닐 포스 피노) 사이클로 펜타 [K] (PH 2 P) 3 C (5) H 2] 및 N 헤테로 카르 벤 -1,3,4,5- tetramethylimidazole -2- 일리 덴 (ME NHC 째 )은 문헌의 절차에 따라 합성하고, 후자는 사용 전에 승화시켰다. 9, 13의 시클로 헥센은 CAH이 건조 증류 제거하고 사용하기 전에 탈기시켰다. 아세토 니트릴 3-D (CD 3 CN) 및 디클로로 메탄 (D2) (CD 2 CL 2) 오산화 인상에서 건조시키고, 사용 전에 탈기시켰다. 규조토는 사용하기 전에 150 ºC 밤새 오븐에서 건조시켰다. 수신 된 모든 다른 시약을 사용 하였다. [dppeP] 1. 합성 어 [br] <ol><li> 디무수 약 40 ㎖ 중의 1,2- 비스 (디 페닐 포스 피노) 에탄 (dppe)의 issolve 1.00 g는 고무 격막이 장착 불활성 가스 하에서, 250 mL 쉴 렝크 (schlenk) 플라스크에 디클로로 메탄 (DCM)을 탈기. </li><li> 주사기 나 캐 뉼러를 전송함으로써, dppe의 교반 용액을 포함하는 쉬 렌크 플라스크에 건조, 탈기, 사이클로 헥센의 2.53 ml를 추가합니다. </li><li> 이 용액에, 주사기를 통해 PBR 3 0.26를 가하여 격렬하게 교반하면서 적가 하였다. 용액은 즉시 20 분 동안 용액을 교반 한 후 옅은 황색, 백색 침전물이 형성됨을 설정한다. 반응이 몇 시간 또는 하룻밤 동안 교반 할 수 있습니다. </li><li> 프릿 플라스크 침전물을 제거하기 위해 1 인치 두께의 규조토 플러그 얹어 통해 몇 시간 동안 교반 또는 하룻밤 후, 반응 혼합물을 필터. </li><li> 생성 된 용액을 수집하고 쉬 렌크 라인에 진공하에 DCM을 제거합니다. </li><li> 얻어진 오일을 테트라 하이드로 퓨란 중 약 75 ㎖ (THF)을 첨가하는 동안 성격렬 irring (또는 초음파 처리)을 백색 고체로서 생성물을 침전시킨다. </li><li> 즉시 백색 침전물을 형성 한 후, 불활성 분위기 하에서 프릿 플라스크에 여과를 통해 수집합니다. 즉시 고체를 수집하고, 30 분 동안 교반 현탁액을 두지 마십시오. </li><li> 일단 수집 순도를 확인하기 위해 31 P, 1 H, 13 C NMR을 얻기 위해 CD이 CL 2 CDCl3 중의 [브롬] dppeP] 소량 녹인다. [dppeP] [브롬]는 불활성 분위기에서 무기한 저장, 또는 벤치 탑에 몇 주 동안 할 수있다. (6) </li></ol> [dppeP] 2. 합성 BPH 4] <ol><li> 쉬 렌크 플라스크에, DCM 5ml에 [dppeP] [브롬] 염 0.5 g을 녹여. 질소 하에서이 용액을 교반 하였다. 이어서, THF 5 ml의 테트라 페닐 보레이트 나트륨 0.35 g을 추가한다. </li><li> 이 솔루션은 미세한 침전물이 형성 될 때까지, 밤새 몇 시간 동안 교반 할 수 있습니다. </li><li> 의 S를 원심 분리기uspension 침전물 (KBr을)를 제거하고 [dppeP] BPH 4] 백색 분말로서 수득 감압하에 용매를 제거한다. </li></ol> 3. 합성 [나 NHC 나 2 P] [BPH 4] <ol><li> 0.200 나 NHC의 g 나와 불활성 분위기 하에서 교반 막대와 100 ㎖ 쉬 렌크 플라스크를 넣습니다. </li><li> 불활성 분위기 하에서 [dppeP] [BPH 4]의 0.603 g을 100 ml의 둥근 바닥 플라스크를 넣습니다. </li><li> 나의 0.200 g NHC 나와 시작 자석 교반을 포함하는 쉬 렌크 플라스크에 THF의 정맥 전송 20 ㎖. </li><li> 정맥 전송은 20 dppeP] [BPH 4]의 0.603 g과 100 ㎖ 둥근 바닥 플라스크에 THF ml의 용해 될 때까지 교반한다. </li><li> 정맥은 [dppeP] [BPH 4] THF의 THF에 나 NHC 날의 교반 솔루션의 솔루션을 전송하고 황색 용액을 1 시간 동안 교반 할 수 있습니다. </li><li> 노란색의 농축감압하에 원래 부피 (13 mL)을 1/3 olution. </li><li> 황색 생성물의 침전을 개시하고 생성 된 현탁액을 20 분 동안 교반하도록 교반 농축 용액에 디 에틸 에테르 (ET 2 O) (40 ml)에 추가한다. </li><li> 쉬 렌크 라인에 100 ㎖ 쉬 렌크 플라스크에 부착 장착 된 밀봉 프릿을 놓고 플라스크를 배기 진공을 사용하고 슐렉 라인에서 질소로 플라스크를 리필하여 불활성 분위기를 만들 수 있습니다. 5 분 동안 피난 불활성 분위기를 보장하기 위해, 질소로 3 회 재충전. </li><li> 캐 뉼러 장치에 잇 2 O 현탁액을 전송하고, 침전물을 필터링. </li><li> 잇 2 O 3 회 10 ml의 침전물을 세척하고 침전물이 2 시간 동안 감압하에 건조 할 수 있습니다. </li><li> ) 옵션은 여과 및 세척이 dppe을 재결정 질소 하에서 천천히 증발하도록 허용합니다. 헥산 건조 최소량으로 결정을 세척하고, 수집재사용 결정. </li></ol> (박사 2 P) C 5 H 2 (박사 2 P) (2) (4) 합성 P <ol><li> 불활성 분위기에서 150 ㎖의 쉬 렌크 플라스크에 포함 0.484g [dppeP] [브롬]로, 건조 40ml를 추가, THF를 탈기. </li><li> -78 ℃로 현탁액의 온도를 드라이 아이스 / 아세톤 조에서 슈렌 배치. </li><li> 정맥은 0.625g의 THF 용액을 전송 [K] [(박사 2 P) 3 C 5 H 2] 둥근 바닥 플라스크에, [dppeP]가 포함 된 쉬 렌크 플래시에 어 [br]. </li><li> 첨가가 완료되면, 아세톤 조에서 쉴 렌크 플라스크를 제거하고 실온으로 가온 할 수있다. 2 시간 동안 교반 한 후, 용액을 백색 침전물 선물을 담황색 것이다. </li><li> 흰색 침전물 (KBr을)를 제거하기 위해, 150 ml의 쉬 렌크 플라스크가 장착 된 공기가없는 융해 필터에 정지를 전송합니다. </li><li> 노란색 솔루션을 수집하고 진공하에 THF를 제거합니다. </li><li> 80:20 추가건조 탈기 된 디 에틸 에테르의 혼합물 : 얻어진 오일 펜탄, 20 분 동안 교반한다. </li><li> 제품을 수집 (박사 2 P) C 5 H 2 (박사 2 P)이 P 공기 무료, 프릿 플라스크를 통해 정지를 필터링하여 옅은 노란색 침전물있다. 나머지 에테르 / 펜탄 용액 dppe 불순물을 포함하고 폐기 될 수 있거나 또는 용매를 진공 또한 사용 수집 dppe하에 제거 될 수있다. </li></ol>

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저자는 공개 아무것도 없어.

결정 구조 및 멀티 NMR은 핵 (31 P, 1 H, 13 C) 연결성을 확인하기 위해보고 된 모든 제품을 얻었다. 전기 분무 이온화 질량 분석법은 양이온의 존재를 확인하는 데 사용하고, 원소 분석은 샘플의 분석 순도를 확인 하였다. 모든 반응 또는 분해시 생성되는 부산물 전혀 예상치 못한이 형성되지 않도록 공기가없는 건조한 환경에서 수행하는 것이 필수적이다...

비정상적으로 낮은 산화 또는 원자가 상태에서 전형 원소의 화학은 지난 20 년 동안 상당한 관심의 영역이었다. 일을 제외하고 독특한 결합과 구조에서 발생하는 근본적인 관심에서, 이러한 화합물은 종종 매우 다른 반응성을 표시 그들의 전형적인 산화 상태의 대응들. 이러한 의미에서, 이들은보다 복잡한 주족 원소 함유 물질을 구축하는 시약으로서 상당한 잠재력을 제공한다. 분자를 포함하는 저 가의 인의 랜드 마크 클래스는 먼저 1980 년대에 Schmidpeter에 의해보고되었다 &quot;triphosphenium&quot;양이온이다. 2보다 안정적인 변종이에서 내장 된 이들 이온은,이 phosphonio 치환기에 의해 결찰 dicoordinate의 인 (I) 이온 기능 . 킬레이트 프레임 워크 3,4 우리 그룹은 triphosphenium 할라이드 염의 합성 최적화 5있다 - 7가이러한 안정한 화합물 다용도 P의 + 전송 인 (I)의 제어 된 합성을위한 유용한 제제 함유 올리고머 8 양쪽 성 이온, 9 phosphamethine 시아닌 염료 있음. 10,11 이러한 화합물의 원래의 합성은 종종 위험한 인을 포함하지만 입증 시약을 함유 및 / 또는 높은 환원 조건, 우리가 제시 제어 경로는 안전, P 원자 효율적이고 편리하다. 염료로서 사용될 수있다 고순도 재료에있어서의 결과는, 전이 금속 착물과 더 복잡한 인 함유 종 전구체 리간드.

<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)

우리는 본원 triphosphenium 브로마이드 염 최적화 합성을 제시한다. 그렇다 다목적 복분해되는 시약이 비정상적으로 낮은 안정 가의 - 인 - 함유 화합물의 유용한 P + 이동제로서 작용한다. 전통적인 방법에 액세스하기 위해 사용될 달리 인 보통 자연 발화성 인 - 함유 전구체 (백색 인, 트리스 (트리메틸 실릴) 포스 핀 등), 또는 강한 환원제 (알칼리 금속 칼륨, 흑연 등)을 필요로 종 전류를 둘러 좌표 접근 방식은 자연 발화성 또는 폭발성 시약을 포함하지 않는 기본적인 공기가없는 합성 교육 학부에 의해 우수한 수익률에 큰 규모 (&gt; 20g)을 수행 할 수 있습니다. 브롬 대 이온 용이 원하는 특성 및 반응성을 가진 물질을 얻기 위해 일반적인 염 복분해 시약을 이용한 (이하 설명) 페닐 붕산과 같은 다른 음이온으로 교환된다. 이 P +의 전달 (A)의 다 기능성pproach 용이 각각 양성 이온을 함유하는 NHC 안정화 인 (I) 양이온 인 (I)을 수득 중립 스포 스핀 변위 각의 N 헤테로 카르 벤 및 음이온 스포 스핀, 이러한 triphosphenium 전구체의 반응에 의해 예시 .

저 가의 인 (I)의 소스를 함유하는 안정한 염 ([dppeP] 브롬]) 과량의 시클로 헥센의 존재 diphenylphosphinoethane (dppe)에 PBR 3의 첨가에 의해 용이하게 (도 1)를 합성 할 수있다 (6). 반응의 워크 업 후, 31 P NMR 스펙트럼은 상당히 -220 ppm으로 차폐 삼중 신호의 존재는 50 ppm에서 이중선 신호를 나타낸다. 핵 사이의 강한 결합은 5...

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.

Triphosphenium 브로마이드 소금의 제조 및 반응성 : 인의 편리하고 안정적인 소스 (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 조회수.  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.

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

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.

온화한 반응 조건 하에서 팔라듐 - 디클로로 {비스 [(phosphinetriyl) tripiperidine 1,1 &#39;, 1 &#39;&#39;]} 의해 촉매 Mizoroki-헥 크로스 커플 링 반응

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 ...

연구

화학

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.

화이트 인의 활성화에 카르 보닐 장식 카르 벤의 제조 및 사용

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.

루테늄의 시리즈의 합성, 특성 및 반응성<em&gt; N</em&gt; -triphos<sup&gt; 박사</sup&gt; 단지

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

Optimized Procedure for Determining the Adsorption of Phosphonates onto Granular Ferric Hydroxide using a Miniaturized Phosphorus Determination Method

This paper introduces a procedure to investigate the adsorption of phosphonates onto iron-containing filter materials, particularly granular ferric hydroxide (GFH), with little effort and high reliability. The phosphonate, e.g., nitrilotrimethylphosphonic acid (NTMP), is brought into contact with the GFH in a rotator in a solution buffered by an organic acid (e.g., acetic acid) or Good buffer (e.g., 2-(N-morpholino)ethanesulfonic acid) [MES] and N-cyclohexyl-2-hydroxyl-3-aminopropanesulfonic acid [CAPSO]) in a concentration of 10 mM for a specific time in 50 mL centrifuge tubes. Subsequently, after membrane filtration (0.45 &#181;m pore size), the total phosphorus (total P) concentration is measured using a specifically developed determination method (ISOmini). This method is a modification and simplification of the ISO 6878 method: a 4 mL sample is mixed with H2SO4 and K2S2O8 in a screw cap vial, heated to 148-150 &#176;C for 1 h and then mixed with NaOH, ascorbic acid and acidified molybdate with antimony(III) (final volume of 10 mL) to produce a blue complex. The color intensity, which is linearly proportional to the phosphorus concentration, is measured spectrophotometrically (880 nm). It is demonstrated that the buffer concentration used has no significant effect on the adsorption of phosphonate between pH 4 and 12. The buffers, therefore, do not compete with the phosphonate for adsorption sites. Furthermore, the relatively high concentration of the buffer requires a higher dosage concentration of oxidizing agent (K2S2O8) for digestion than that specified in ISO 6878, which, together with the NaOH dosage, is matched to each buffer. Despite the simplification, the ISOmini method does not lose any of its accuracy compared to the standardized method.

This paper introduces a procedure to investigate the adsorption of phosphonates onto iron-containing filter materials, particularly granular ferric hydroxide, with little effort and high reliability. In a buffered solution, the phosphonate is brought into contact with the adsorbent using a rotator and then analyzed via a miniaturized phosphorus determination method.

소형 인 결정 방법을 사용 하 여 세분화 된 제 2 철 수산화에 Phosphonates의 흡착을 결정 하기 위한 최적화 된 절차

This paper introduces a procedure to investigate the adsorption of phosphonates onto iron-containing filter materials, particularly granular ferric ...

환경과학

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.

고체 및 솔루션 기반의 기술 결합 : 합성 및 Chalcogenidoplumbates의 반응성 (II 또는 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 ...

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the activation of a broad variety of organic halides, including unactivated ones. These can then participate in various radical transformations such as reduction and cyclization reactions, as well as in the direct arylation of several (hetero)arenes. These transformations provide a straightforward access to a range of small molecules of interest in synthetic chemistry, as well as to biologically active natural products. Altogether, [(DPEPhos)(bcp)Cu]PF6 acts as a convenient photoredox catalyst which appears to be an attractive, cheap and complementary alternative to the state-of-the-art iridium- and ruthenium-based photoredox catalysts. Here, we report a detailed protocol for the synthesis of [(DPEPhos)(bcp)Cu]PF6, as well as NMR and spectroscopic characterizations, and we illustrate its use in synthetic chemistry for the direct arylation of (hetero)arenes and radical cyclization of organic halides. In particular, the direct arylation of N-methylpyrrole with 4-iodobenzonitrile to afford&#160;4-(1-methyl-1H-pyrrol-2-yl)benzonitrile and the radical cyclization of N-benzoyl-N-[(2-iodoquinolin-3-yl)methyl]cyanamide to afford natural product luotonin A are detailed. The scope and limitations of this copper-based photoredox catalyst are also briefly discussed.

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Detailed and general protocols are presented for the synthesis of [(DPEPhos)(bcp)Cu]PF6, a general copper-based photoredox catalyst, and for its use in synthetic chemistry for the direct arylation of C-H bonds in (hetero)arenes and radical cyclization of organic halides.

[(Bcp)] PF6: 일반적이 고 광범위 하 게 적용 가능한 구리 기반 포토에도 x 촉매

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the ...

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Dynamic solution nuclear magnetic resonance (NMR) spectroscopy is the typical method of characterizing the dynamic rearrangements of atoms within the coordination sphere for transition metal polyhydride complexes. Line shape fitting of the dynamic NMR spectra can lead to estimates for the activation parameters of the dynamic rearrangement processes. A combination of dynamic 31P-{1H} NMR spectroscopy of metal-bound phosphorus atoms with dynamic 1H-{31P} NMR spectroscopy of hydride ligands may identify hydride ligand rearrangements that occur in conjunction with a phosphorus atom rearrangement. For molecules that exhibit such a coupled pair of rearrangements, dynamic NMR spectroscopy can be used to test theoretical models for the ligand rearrangements. Dynamic 1H-{31P} NMR spectroscopy and line shape fitting can also identify the presence of an exchange process that moves a specific hydride ligand beyond the metal&#39;s inner coordination sphere through a proton exchange with a solvent molecule such as adventitious water. The preparation of a new compound, ReH5(PPh3)2(sec-butyl amine), that exemplifies multiple dynamic rearrangement processes is presented along with line shape fitting of dynamic NMR spectra of the complex. Line shape fitting results can be analyzed by the Eyring equation to estimate the activation parameters for the identified dynamic processes.

Line shape analysis of NMR spectra collected over a range of temperatures serves as a guide for the rearrangement of inner coordination-sphere atoms at a chiral, eight-coordinate, rhenium(V) polyhydride complex, ReH5(PPh3)2(sec-butyl amine). Line shape analysis is also used to determine the activation parameters &#916;H&#8225;, &#916;S&#8225;, and &#916;G&#8225; for those atom rearrangements.

키랄 레늄 폴리하이드라이드 복합체에서 배위 구 재배열을 특성화하기 위한 동적 NMR 스펙트럼의 선 모양 분석

Dynamic solution nuclear magnetic resonance (NMR) spectroscopy is the typical method of characterizing the dynamic rearrangements of atoms within the ...

Multitopic Phosphine Linker에서 Low-Valent MOF의 합성

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.

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

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.

Multitopic Phosphine Linkers로부터 저가 금속-유기 프레임워크의 합성을 위한 실험적 접근법

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

Triphosphenium 브로마이드 소금의 제조 및 반응성 : 인의 편리하고 안정적인 소스 (I)

요약

더 많은 비디오 탐색

이 비디오의 챕터

온화한 반응 조건 하에서 팔라듐 - 디클로로 {비스 [(phosphinetriyl) tripiperidine 1,1 ', 1 '']} 의해 촉매 Mizoroki-헥 크로스 커플 링 반응

화이트 인의 활성화에 카르 보닐 장식 카르 벤의 제조 및 사용

루테늄의 시리즈의 합성, 특성 및 반응성

소형 인 결정 방법을 사용 하 여 세분화 된 제 2 철 수산화에 Phosphonates의 흡착을 결정 하기 위한 최적화 된 절차

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[(Bcp)] PF₆: 일반적이 고 광범위 하 게 적용 가능한 구리 기반 포토에도 x 촉매

키랄 레늄 폴리하이드라이드 복합체에서 배위 구 재배열을 특성화하기 위한 동적 NMR 스펙트럼의 선 모양 분석

Multitopic Phosphine Linkers로부터 저가 금속-유기 프레임워크의 합성을 위한 실험적 접근법

Multitopic Phosphine Linkers로부터 저가 금속-유기 프레임워크의 합성을 위한 실험적 접근법

Multitopic Phosphine Linkers로부터 저가 금속-유기 프레임워크의 합성을 위한 실험적 접근법