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:氘代溶剂根据文献程序在必要时，所有其它溶剂干燥的一系列Grubbs&#39;型柱12和在使用之前脱气干燥。钾1,2,4-三（二苯基膦基）环戊二烯[K] [（PH 2×P）3 C 5 H 2]和N-杂环卡宾-1,3,4,5- tetramethylimidazole -2-亚基（ 我 NHC 我 ）根据文献方法合成的，后者在使用前升华。9,13环己烯经氢化钙2上干燥，蒸馏，使用前脱气。乙腈- d 3处（CD 3 CN）和二氯甲烷- D 2（CD 2 Cl 2中）用五氧化二磷干燥，并在使用前脱气。硅藻土在150ºC烘箱使用过夜之前干燥。原样使用的所有其它的试剂。 1.合成[dppeP] [BR] <ol><li> ðissolve 1.00克在约40毫升无水的1,2-双（二苯基膦基）乙烷（DPPE），在250毫升Schlenk烧瓶脱气二氯甲烷（DCM），在惰性气体下，配备有橡胶隔片。 </li><li>通过注射器或套管转移，添加2.53毫升干燥，脱气，环己烯的含有DPPE的搅拌的溶液中的Schlenk烧瓶中。 </li><li>到该溶液中，通过注射器添加0.26毫升PBR 3，在剧烈搅拌下逐滴。该溶液应立即将浅黄色，并形成白色沉淀搅拌该溶液20分钟后。使反应搅拌几个小时或过夜。 </li><li>搅拌数小时或过夜后，过滤该反应混合物通过一个烧结烧瓶用一英寸厚的硅藻土塞淋上以除去沉淀物。 </li><li>收集得到的溶液，除去DCM在真空下于一的Schlenk线。 </li><li>向所得的油中，添加约75毫升四氢呋喃（THF）中而STirring大力（或声波处理），以沉淀出产物，为白色固体。 </li><li>白色沉淀物形成后，立即通过过滤收集它与惰性气氛下烧结烧瓶中。收集固体立即，不离开悬挂搅拌30分钟以上。 </li><li>一旦收集，溶解[BR]的[dppeP]少量的CD 2 Cl 2 中或CDCL 3，以获得31 P，1 H和13 C-NMR确认纯度。 [dppeP] [BR]可以无限期地保存在惰性气氛中，或用于在台式几个星期。6 </li></ol> 2. [dppeP]合成[BPH 4] <ol><li>溶解0.5克[dppeP] [BR]盐的5ml DCM中，在Schlenk烧瓶。搅拌在氮气下将溶液。然后，在5毫升THF中添加0.35克四苯基硼酸钠。 </li><li>让溶液搅拌几个小时或过夜，直至微细的析出物的形式。 </li><li>离心机在Suspension消除沉淀物（溴化钾）并减压除去溶剂，得到[dppeP] [BPH 4]，为白色粉末。 </li></ol> 3.合成[ 我 NHC 我 2 P] [BPH 4] <ol><li>装入100毫升Schlenk烧瓶与0.200克我 NHC的我和惰性气氛下搅拌棒。 </li><li>加载的100毫升圆底烧瓶中0.603克的[dppeP] [4 BPH]在惰性气氛下。 </li><li>套管转移20ml THF中含0.200克我的NHC 我和开始磁力搅拌的Schlenk烧瓶。 </li><li>套管转移20ml THF中，以100毫升圆底烧瓶中0.603克的[dppeP] [4 BPH]并搅拌直至溶解。 </li><li>套管转移的[dppeP] [BPH 4]的THF到我 NHC 我的在THF中的搅拌溶液的溶液，并允许将黄色溶液搅拌1小时。 </li><li>浓缩黄Solution到第三减压原始体积（13毫升）中的。 </li><li>乙醚（Et 2 O等）（40毫升）添加到搅拌浓缩液以引发黄色产物沉淀，并允许将得到的悬浮液搅拌20分钟。 </li><li>放置装附密封玻璃料上的Schlenk线的100毫升的Schlenk烧瓶中，并通过使用真空抽空该烧瓶并再填充与来自施莱克线氮气将烧瓶创建惰性气氛。疏散5分钟，并用氮气再填充3次，以确保惰性气氛。 </li><li>套管转移的Et 2 O悬浮到装置并过滤沉淀物。 </li><li>用10毫升的Et 2 O三次洗涤沉淀物，并允许该沉淀物在减压下干燥2小时。 </li><li>可选）允许滤液和洗液缓慢蒸发氮气下再结晶DPPE。用己烷，干的最小量洗涤晶体，并收集晶体重新使用。 </li></ol> 4.（pH为2 P）C 5 H 2（PH 2 P）2合成对<ol><li>在惰性气氛的150毫升的Schlenk烧瓶中含有0.484克[dppeP] [BR]，加40毫升干燥，脱气的THF。 </li><li>放置的Schlenk在干冰/丙酮浴中向悬浮液冷却至-78℃。 </li><li>套管转移0.625克的THF溶液[K] [（PH 2×P）3 C 5 H 2]在圆底烧瓶中，向含有[dppeP]将舒伦克闪光灯[BR]。 </li><li>当加料完成后，从丙酮浴中取出Schlenk烧瓶，并允许温热至室温。搅拌2小时后，将溶液将浅黄色带有白色沉淀物存在。 </li><li>转移悬浮液到装有150ml的Schlenk烧瓶一个无空气多孔过滤器，以除去白色沉淀物（溴化钾）。 </li><li>收集黄色溶液，并在真空下除去THF。 </li><li>添加80:20干燥和脱气乙醚混合物:戊烷向所得油并搅拌20分钟。 </li><li>收集产物（PH 2 P）C 5 H 2（PH 2 P）2个 P为通过一个自由空气，烧结烧瓶过滤该悬浮液一浅黄色沉淀。剩余的乙醚/戊烷溶液含有DPPE杂质，并且可以被丢弃，或者可以真空并收集用于进一步使用的DPPE下除去溶剂。 </li></ol>

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作者什么都没有透露。

为报告，以确认连接的所有产品，得到的晶体结构和多核NMR（31 P，1 H和13 C）。电电离质谱分析法被用来确认阳离子的存在和用元素分析来确认样品的分析纯度。 至关重要的是，所有的反应是在干燥的无空气的环境中进行，以确保没有意外的副产物或分解产物形成的。使用DPPE略有过剩，以及环己烯的过量（10当量）是必要的，以确保[dppeP] [BR]良好收益。 有本文中所描述的技术的没有大的限制。与[dppeP] [BR]配体置换反应仅限于对从[dppeP] [BR]分子置换DPPE足够供体能力的配体。尽管如此，这种方法的显著优势是controlle"P +"的d-释放未经意料之外副产物的产生或使用苛刻的试剂。因此，这种方法可以在将来被用来产生含P 我部分新分子。

在非常低的氧化或价态主族元素的化学已从其独特的粘合和结构引起的根本利益，在过去的二十年一直显著兴趣的领域。1除了，这些化合物常常显示从非常不同的反应性他们那些较为典型的氧化态同行。在这个意义上说，他们提供显著潜力试剂建造更复杂的主基团的元素的材料。 含分子具有里程碑意义的类低价的磷是这是首次由Schmidpeter 20世纪80年代报"triphosphenium"阳离子。2这些离子配有两个phosphonio取代连接一个dicoordinate磷（I）离子，具有更稳定的变种从建。螯合框架3,4我们集团优化triphosphenium卤盐的合成5 - 7，具有证明，这些稳定化合物是对于磷（I）的受控合成有用多功能P +转移剂的含低聚物，8两性离子，9和phosphamethine花青染料。-10,11-虽然这类化合物的原始合成通常涉及危险磷含的试剂和/或高度减小条件下，我们目前的控制路线是安全的，P-原子高效，方便。在高纯度材料的方法，结果可使用的染料，配体对过渡金属配合物和用于更复杂的含磷物质的前体。

<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)

我们在此提出一个triphosphenium溴化物盐的优化合成。除了是一种多功能复分解试剂，这种异常稳定含有低原子价磷化合物作为一种有用的 P +转移剂。不同于传统的方法中使用以访问低坐标磷物种通常需要自燃含磷前体（白磷，三（三甲基甲硅烷）膦等 ），或苛刻还原剂（碱金属，钾石墨等 ），目前方法不涉及引火或爆炸性的试剂，并可以在良好的收益大尺度（&gt; 20克）通过大学生基本无空气的合成训练来完成。溴化物抗衡离子可容易地使用典型的盐复分解试剂以获得具有所需性质和反应性材料以外的阴离子，例如四苯基硼酸盐（本文中所描述）交换。这种P +转让的多功能性接近角通过用N-杂环卡宾和阴离子双膦，其中每一个容易置换中性二膦，得到NHC稳定磷（I）的含有两性离子的阳离子和磷（I）中，分别这些triphosphenium前体的反应例举。

含有低价的磷（I）的源的稳定盐（[dppeP] [BR]）可以容易地通过在过量的环己烯的存在下，加成PBR 3到二苯基膦乙烷（DPPE）合成（ 图1）6。 在反应的后处理，31 P NMR光谱表明在-220 ppm的显著屏蔽三重信号的存在，并在50 ppm的一个双峰信号。原子核之间的强耦合500赫兹（ 图2）的数量级上观察到。 单晶可以从浓缩乙腈或二氯甲烷溶液和单晶X射线衍射分析来生长表明[dppeP] [BR]具有与存在于非对称单元中的两个式的单元（ 图4）的离子分离结构。溴离子可以为反应性较低的阴离子，SUC交换H作为三氟甲磺酸酯（三氟甲磺酸酯，光学传递函数），或四苯基硼酸（BPH 4）。该产物的31 P NMR光谱几乎相同，所述起始材料[dppeP] [BR]（ 图3）的。 的[dppeP]此外[BPH 4]含卡宾我 NHC 我的结果在螯合双-膦的位移的两当量的更强烈供NHC配体的溶液，并生成黄色phosphamethine花青染料[ 我 NHC 我 2个 P ] [BPH 4]（ 图1）。因为[ 我 NHC 我 2个 P] [BPH 4]可溶于THF但在乙醚不溶，后者用于去除二膦副产物，这是在大多数溶剂高度可溶的。一旦通过过滤分离，洗涤和干燥，[ 我 NHC 我 2个 P] [BPH 4]作为得到分析纯黄色粉末。这种材料溶解于乙腈-D 3的31 P NMR光谱在-113 ppm的，这是显著相对于典型phosphaalkenes屏蔽（参照31 P NMRδ对于p -mesityldiphenylmethylenephosphine = 233.06 ppm的14），这是相一致有单峰信号与磷（I）的分配（ 图5）。 同样地，相对长CP键长，急性中共角度和杂环的扭转从在晶体结构中观察到的中共平面[ 我 NHC 我 2个 P] [BPH 4]（ 图6）也与磷最一致（Ⅰ）的描述。除了其潜在的应用作为染料，如化合物〔 我 NHC 我 2个 P] [BPH 4]也被证明是有用的配体和试剂对于CA的制备一种类型是在催化应用中有用组分的tionic膦。15 与[dppeP] [BR]产率1化学计量比（PH 2 P）C 5 H 2（PH 2 P）2个 P以定量产率（:钾1,2,4-三（二苯基膦基）环戊二烯在1反应图1）9。从该反应中唯一的副产物，即溴化钾和DPPE，可以通过在THF抽滤和乙醚/戊烷分别被删除。从（PH 2 P）C 5 H 2（PH 2 P）2个 P在光盘2 Cl 2中（ 图7）显示在-174 ppm的三重信号的存在，由于浓缩液中得到的31 P NMR谱所述dicoordinate磷（I）的中心，在-16.9 ppm的用于在主链上的pH值2个 P片段的单峰信号和双峰信号归属于两个pH &lt;该螯合磷（I）中心副&gt; 2个P组。 从单晶X射线衍射分析，得到这种分子的这种结构示于图8。晶体可通过DCM中，THF中的浓溶液，或者甚至乙醚的稀溶液缓慢蒸发生长。 （PH 2 P）C 5 H 2（PH 2 P）2个 P的配体化学是有意义的，因为分子具有三种不同类型的供区与它可能与金属交互:它的特点是磷化氢现场，phosphide-像现场，和一个环戊二烯站点9 <img alt="图1" src="/files/ftp_upload/55021/55021fig1.jpg" /> 图1. PBR 3和环己烯DPPE的反应，[4 BPH]与我 [dppeP] NHC Me和]与dppeP] [BR [K] [（PH 2 P）3 C 5 H 2]。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图2" src="/files/ftp_upload/55021/55021fig2.jpg" /> 图2. 31 P（A），1 H（B）和 13 C（C）NMR [BR]的[dppeP]光谱收集 在协议中描述的方法制备 CD 2 Cl 2 中 。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig2large.jpg" target="_blank">请点击此处查看大图版本这个数字。</a> <img alt="图3" src="/files/ftp_upload/55021/55021fig3.jpg" /> <s仲&gt;图3 31 P（A），1 H（B）中，11 B（C），和 13 C（D）的[dppeP] [BPH 4]收集在光盘 2 Cl 2 中 在协议中描述的方法制备。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig3large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图4" src="/files/ftp_upload/55021/55021fig4.jpg" /> 图4. [BR]（A）和[dppeP] [BPH 4]（ 二）[dppeP] 分子结构 。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig4large.jpg" target="_blank">请点击此处查看次的放大版本</a>是图。 <img alt="图5" src="/files/ftp_upload/55021/55021fig5.jpg" /> 图5. 31 P（A），1 H（B）中，11 B（C）和 13 C（D）的核磁共振光谱[ 我 NHC 我 2个 P] [BPH 4]在光盘 3 收集在所描述的CN制备协议。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig5large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图6" src="/files/ftp_upload/55021/55021fig6.jpg" /> 图6。<html>分子结构[ 我 NHC 我 2 P] [BPH 4]。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig6large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图7" src="/files/ftp_upload/55021/55021fig7.jpg" /> 图7. 31 P（A），1 H（B）和 13 C（C）的核磁共振谱（PH 2 P）C 5 H 2（PH 2 P）2个 P收集在光盘 2 Cl 2 作中所述制备的协议。//ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig7large.jpg"目标="_空白"&gt;点击此处查看该图的放大版本。 <img alt="图8" src="/files/ftp_upload/55021/55021fig8.jpg" /> 图8.分子结构（PH 2 P）C 5 H 2（PH 2 P）2 P. <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55021/55021fig8large.jpg" target="_blank">请点击此处查看该图的放大版本。</a>

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.

制备及反应性的Triphosphenium溴化物盐:磷方便稳定来源（I）

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

preparation-reactivity-triphosphenium-bromide-salt-convenient-stable

Nanyang Technological University

Research

JoVE Journal

Chemistry

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

7.7K 次观看.  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.

视频: 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.

核苷三磷酸 - 从合成到生化特征

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

科研

化学

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-哎呀交叉偶联反应由二氯{双[1,1&#39;，1&#39;&#39;  - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

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.

羰基饰卡宾的白色磷的活化制备方法和用途

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.

一系列钌的合成，表征和反应<em&gt;Ñ</em&gt; -triphos<sup&gt;博士</sup&gt;配合

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.

用小型化磷测定法测定膦酸在粒状氢氧化铁上吸附的优化方法

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

环境科学

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.

结合固态和基于解决方案的技术合成及Chalcogenidoplumbates的反应（II或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.

高纯度对称 Dialkylphosphinic 酸萃取的合成

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 ...

从多主题膦接头合成低价 MOF

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.

作者聚焦:从多主题膦接头合成低价金属有机框架的实验方法  

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.

多位膦接头合成低价金属有机骨架的实验方法

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

制备及反应性的Triphosphenium溴化物盐:磷方便稳定来源（I）

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此视频中的章节

核苷三磷酸 - 从合成到生化特征

Mizoroki-哎呀交叉偶联反应由二氯{双[1,1'，1'' - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

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