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.

注：必要な場合重水素化溶媒は、文献の手順に従って乾燥させ、そして他のすべての溶媒をGrubbs&#39;型コラム12の系列上で乾燥し、使用前に脱気しました。カリウム1,2,4-トリス（ジフェニルホスフィノ）シクロペンタ[K] [（PH 2 P）3 C 5 H 2]、N-複素環カルベン-1,3,4,5- tetramethylimidazole -2-イリデン（ME NHC ミー ）は、文献の手順に従って合成し、後者は、使用前に昇華させた。9,13シクロヘキセンは、CaH 2上で乾燥させ、蒸留し、使用前に脱気しました。アセトニトリルD 3（CD 3 CN）およびジクロロメタン-D 2（CD 2 Cl 2）で五酸化リン上で乾燥し、使用前に脱気しました。珪藻土は、使用する前に一晩150ºCのオーブンで乾燥させました。受信されたように、すべての他の試薬を使用しました。 【dppeP] [BR] 1.合成<ol><li> D無水の約40 ml溶液に、1,2-ビス（ジフェニルホスフィノ）エタン（DPPE）のissolve 1.00 gを、ゴム隔膜を装備し、不活性ガス下で250mlのシュレンクフラスコに、ジクロロメタン（DCM）を脱気しました。 </li><li>注射器またはカニューレ転送することで、DPPEの撹拌溶液を含むシュレンクフラスコに乾燥、脱気し、シクロヘキセンの2.53ミリリットルを追加します。 </li><li>この溶液に、注射器、激しく撹拌しながら滴下経由のPBr 3の0.26ミリリットルを追加します。溶液は直ちに20分間溶液を撹拌した後、淡黄色、白色の沈殿物が形成さを有効にしてください。反応は数時間または一晩攪拌します。 </li><li>数時間または一晩撹拌した後、フリット付きフラスコから反応混合物をフィルタリングして沈殿物を除去するために、1インチの厚さの珪藻土のプラグをトッピング。 </li><li>得られた溶液を収集し、シュレンクライン上で真空下でDCMを除去します。 </li><li>得られたオイルに、STながら、テトラヒドロフランの約75ミリリットル（THF）を追加白色の固体として生成物を沈殿させ、激しくirring（または超音波処理）。 </li><li>すぐに白い沈殿物が形成した後、不活性雰囲気下でフリットフラスコに濾過して、それを収集します。すぐに固体を収集し、30分以上攪拌して懸濁液を放置しないでください。 </li><li>一旦集め、純度を確認するために、31 P、1 Hおよび13 C NMRを得るために、CD 2 Cl 2またはCDCl 3中の[dppeP] [BR]を少量溶解させます。 【dppeP] [BR]は不活性雰囲気中で無期限に保存されている、または卓上に数週間のためにすることができます。6 </li></ol> 【dppeP] [BPH 4]の2合成<ol><li>シュレンクフラスコに、DCM 5mlに[dppeP] [BR]塩0.5gを溶解します。窒素ガス下で溶液を撹拌しました。その後、THF 5ml中のテトラフェニルホウ酸ナトリウムの0.35グラムを追加します。 </li><li>解決策は、微細な沈殿が形成されるまで、数時間または一晩攪拌します。 </li><li>遠心分離機の沈殿物（KBr法）を除去し、白色粉末として[dppeP] [BPH 4]を得、減圧下で溶媒を除去しuspension。 </li></ol> 3.合成【 ミー NHC ミー 2 P] [BPH 4] <ol><li>不活性雰囲気下で私 NHC Meおよび撹拌棒の0.200グラムと100ミリリットルシュレンクフラスコをロードします。 </li><li>不活性雰囲気下で[dppeP] [BPH 4]の0.603グラムで100ミリリットル丸底フラスコをロードします。 </li><li> 私の0.200グラムNHC Meおよび磁気撹拌を開始を含むシュレンクフラスコにカニューレ転送20mlのTHFを。 </li><li> 【dppeP] [BPH 4]の0.603グラムと100ミリリットル丸底フラスコにTHFのカニューレ転送20ミリリットル、溶解するまで撹拌します。 </li><li>カニューレは、[dppeP] [BPH 4] THF中のTHF中のミー NHC 私の撹拌溶液への解決策を転送し、黄色の溶液を1時間撹拌することができます。 </li><li>黄色のコンセントレイト減圧下で元の容量（13ミリリットル）の3分のolution。 </li><li>黄色生成物の沈殿を開始し、得られた懸濁液を20分間撹拌することを可能にする攪拌濃縮液にジエチルエーテル（Et 2 O）（40ml）に加えます。 </li><li>シュレンクライン上の100ミリリットルのシュレンクフラスコに取り付け取り付けられた密封されたフリットを置き、フラスコを真空排気を使用し、シュレックラインから窒素でフラスコを補充することにより、不活性雰囲気を作成します。 5分間排気し、不活性雰囲気を保証するために、窒素を3回補充。 </li><li>カニューレは、装置内のEt 2 Oサスペンションを転送し、沈殿物をフィルタリングします。 </li><li> Et 2 Oで3回10mlで沈殿物を洗浄し、沈殿物を減圧下で2時間乾燥させます。 </li><li>オプション）ろ液および洗浄液がDPPEを再結晶化するために、窒素下でゆっくり蒸発させます。ヘキサン、乾燥最小限の量で結晶を洗浄し、収集再利用のための結晶。 </li></ol> （Phは2 P）C 5 H 2（Phで2 P）2の4の合成P <ol><li>不活性雰囲気中で0.484グラム[dppeP] [BR]を含む150ミリリットルシュレンクフラスコに、乾燥の40ミリリットルを追加し、THFを脱気。 </li><li> -78℃にサスペンションを冷却するために、ドライアイス/アセトン浴中でシュレンクを置きます。 </li><li>カニューレは、[dppeP] [BR]を含むシュレンクフラッシュに、丸底フラスコに0.625グラムのTHF溶液[K] [（Phは2 P）3 C 5 H 2]を転送します。 </li><li>添加が完了したら、アセトン浴からシュレンクフラスコを取り外し、室温まで加温することを可能にします。 2時間攪拌した後、溶液を、白色沈殿物が存在で淡黄色です。 </li><li>白色の沈殿物（KBr法）を除去するために、150ミリリットルのシュレンクフラスコを搭載した空気を含まないフリットフィルタにサスペンションを転送します。 </li><li>黄色の溶液を収集し、真空下でTHFを除去。 </li><li> 80:20を追加乾燥および脱気したジエチルエーテルの混合物：得られた油状物をペンタンで20分間撹拌することを可能にします。 </li><li>生成物を回収（PH 2 P）C 5 H 2（Phで2 P）2 P無空気、フリットフラスコを通して懸濁液を濾過することにより、淡黄色の沈殿物として。残りのエーテル/ペンタン溶液をDPPE不純物を含有し、廃棄してもよいし、溶媒を真空、さらなる使用のために収集DPPE下で除去することができます。 </li></ol>

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著者らは、開示することは何もありません。

結晶構造及び多核NMR（31 P、1 Hおよび13 C）は、接続性を確認するために、報告された全ての製品について得られました。エレクトロスプレーイオン化質量分析は、陽イオンの存在を確認するために使用された、元素分析は、サンプルの分析的純度を確認しました。 すべての反応がまたは分解生成物副産物予期しないが形成されないことを確実にす...

異常に低い酸化または原子価状態での主族元素の化学的性質は、過去20年間の大きな関心のエリアとなっている。1別に独自の結合および構造に起因する根本的な関心から、このような化合物は、しばしば非常に異なる反応性を表示しますそれらのより一般的な酸化状態の対応のもの。この意味で、彼らはより複雑なメイングループ元素含有物質を構築するための試薬としての大きな可能性を提供します。 分子を含む低価のリンのランドマーククラスが最初に1980年代にSchmidpeterによって報告された「triphosphenium」カチオンである。2これらのイオンから構築され、より安定した亜種で、2ホスホニオ置換基により連結したdicoordinateリン（I）イオンを備えています。キレートフレームワーク3,4当社グループはtriphospheniumのハロゲン化物塩の合成を最適化5ている- 7と持っていますこれらの安定な化合物は、リンの制御合成（I）のオリゴマー、8両性イオン、9及びphosphamethineシアニン色素を含有するために有用な多目的のP +移動剤であることを実証した。10,11のこのような化合物の元の合成は、しばしば危険なリンを含むが試薬を含有および/または高還元条件、我々が提示する制御経路は、P-原子効率的、かつ便利、安全です。染料として使用することができる高純度材料のメソッドの結果は、遷移金属錯体と、より複雑なリン含有種の前駆体のためのリガンド。

<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)

私たちは、ここでtriphospheniumの臭化物塩の最適化された合成を提示します。別に多目的なメタセシス試薬であることから、この異常に安定した低価のリン含有化合物は、有用なP +移動剤として作用します。通常発火リン含有前駆体（白リン、トリス（トリメチルシリル）ホスフィンなど ）、または過酷な還元剤（ 等のアルカリ金属、カリウムグラファイト）、電流を必要とする低座標リン種をアクセスするために用いられる従来の方法とは異なりアプローチは、自然発火や爆発の試薬を伴わないと、基本的な空気のない合成訓練を受けた大学生により優れた収率で大きなスケール（&gt; 20グラム）で行うことができます。臭化物対イオンは、容易に所望の特性および反応性を有する材料を得るために、典型的な塩メタセシス試薬を使用して、そのような（本明細書中に記載）テトラフェニルボレートなどの他の陰イオンと交換されます。このPの+転送 aの汎用性pproach容易それぞれ、双性イオンを含むNHC安定化リン（I）のカチオンと、リン（I）を与えるために、中性ビスホスフィンを変位各々がN-複素環カルベンおよびアニオンビスホスフィン、これらtriphosphenium前駆体の反応によって例示されます。

低原子価リン（I）源を含む安定な塩（[dppeP] [BR]）は（ 図1）6過剰シクロヘキセンの存在下でdiphenylphosphinoethaneへのPBr 3を加え（DPPE）によって容易に合成することができます。 反応のワークアップ時に、31 P NMRスペクトルは大幅-220 ppmに遮蔽されているトリプレット信号の存在、および50 ppmの二重のシグナルを?...

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臭化物塩の調製と反応性：リンの便利で安定したソース（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 ビュー.  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.

ビデオ: 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.

温和な反応条件の下でパラジウム - ジクロロ{ビス[（ホスフィントリ）tripiperidine 1,1 &#39;、1&#39;&#39;]}触媒による溝呂木 - ヘッククロスカップリング反応

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 ...

化学

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.

白リンの活性化カルボニル装飾カルベンの調製および使用

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.

ルテニウムのシリーズの合成、キャラクタリゼーションと反応性<em&gt; N</em&gt; -triphos<sup&gt; Phで</sup&gt;錯体

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.

最適化された小型リン定量法を用いた粒状水酸化第二鉄に酸の吸着を確認する手順

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

環境学

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.

組み合わせソリッドステートおよびソリューションベースのテクニック：合成と反応性Chalcogenidoplumbatesの（IIまたは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.

[(DPEPhos) (bcp) Cu]PF6: 一般的で広く適用される銅系 Photoredox 触媒

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.

キラルレニウムポリヒドリド錯体における配位球転位特性評価のための動的NMRスペクトルの線形状解析

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

マルチトピックホスフィンリンカーからの低原子価MOFの合成

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.

著者スポットライト:マルチトピックホスフィンリンカーからの低原子価金属有機フレームワークの合成のための実験的アプローチ  

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.

多位ホスフィンリンカーからの低原子価金属-有機構造体の合成のための実験的アプローチ

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

Triphosphenium臭化物塩の調製と反応性：リンの便利で安定したソース（I）

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温和な反応条件の下でパラジウム - ジクロロ{ビス[（ホスフィントリ）tripiperidine 1,1 '、1'']}触媒による溝呂木 - ヘッククロスカップリング反応

白リンの活性化カルボニル装飾カルベンの調製および使用

ルテニウムのシリーズの合成、キャラクタリゼーションと反応性

最適化された小型リン定量法を用いた粒状水酸化第二鉄に酸の吸着を確認する手順

組み合わせソリッドステートおよびソリューションベースのテクニック：合成と反応性Chalcogenidoplumbatesの（IIまたはIV）

[(DPEPhos) (bcp) Cu]PF₆: 一般的で広く適用される銅系 Photoredox 触媒

キラルレニウムポリヒドリド錯体における配位球転位特性評価のための動的NMRスペクトルの線形状解析

多位ホスフィンリンカーからの低原子価金属-有機構造体の合成のための実験的アプローチ

多位ホスフィンリンカーからの低原子価金属-有機構造体の合成のための実験的アプローチ

多位ホスフィンリンカーからの低原子価金属-有機構造体の合成のための実験的アプローチ