低配位磷烯化合物及其最新进展

总结了有关低配位磷烯化合物(P=C)在合成方法、配位化学特性及应用方面的最新进展.     

一配位有机磷化合物的研究进展

综述了近10年来一配位有机磷化合物的加成反应,Ene反应、聚合反应和络合反应的研究进展。并就其在有机合成中的应用作简要概述。参考文献21篇。     

钯催化芳基乙炔对氧/氮杂苯并降冰片烯开环反应研究

过渡金属催化的碳亲核试剂对氧/氮杂苯并降冰片烯的开环反应是合成氢化萘衍生物的有效方法之一. 在该类反应中, 采用末端炔烃作为碳亲核试剂在反应操作、底物适用范围等多个方面都具有已报道的各种有机金属亲核试剂所不具备的优势. 目前, 对末端炔烃与氧/氮杂苯并降冰片烯的开环反应的研究进展有限, 只有Ni(dppe)Cl₂/ZnCl₂/Zn和手性的Rh两种催化体系被应用到该类反应当中, 但都面临一些不足. 为该类反应开发简单有效的新型催化体系仍然具有重要的意义和价值. 我们通过研究发现: PdCl₂与Xantphos的配合物是芳基乙炔对氧/氮杂苯并降冰片烯亲核开环反应的有效催化剂. 在优化后的反应条件下, 该Pd催化剂具有良好的催化活性和底物适应能力, 能够实现各种取代的芳基乙炔对氧/氮杂苯并降冰片烯的亲核加成, 并以较好的收率生成目标开环产物.     

氮杂炔正离子与环烯反应的机理及取代基效应

用DFT方法研究了氮杂炔正离子[R-C≡N-CH3] 与二环[2,2,1]-2-庚烯的反应机理。所有几何构型用B3LYP/6-31G**基组进行优化,过渡态通过振动分析和内聚反应坐标进行了确认。并在相同基组上研究了当R为不同取代基时的反应变化规律。结果表明该反应为环加成反应,有两条反应途径,产物主要通过能量较低的过渡态TSa生成。当取代基为支链烷烃基团时,反应位垒较大;取代基为直链烷烃基团和苯环时,反应较易进行。     

炔丙基自由基在有机合成化学中的应用

炔烃的合成与转化一直是有机合成化学的一个重要研究内容. 其中, 炔丙位官能化是实现炔烃合成与转化的一个重要途径. 相对于经历阳离子中间体途径的炔丙位官能化反应, 自由基途径的炔丙位官能化反应在最近十年才得以发展, 且与前者也已形成互补之势. 该类炔丙基自由基既能够通过炔丙位的碳杂键断裂生成, 又可通过自由基对1,3-烯炔的加成生成. 同时, 由于炔丙基自由基存在自由基与炔烃的共轭结构, 使得该自由基既能够直接对金属物种加成参与炔丙位的官能化反应, 又能够异构成联烯自由基后对金属物种加成, 继而参与联烯化合物的合成. 此外, 炔丙基自由基还可以被进一步氧化成炔丙基阳离子后参与后续的有机转化. 本综述根据炔丙基自由基所参与的反应类型, 对近年来炔丙位自由基参与的有机反应进行了简要总结.     

仲膦与直链单烯烃反应的原位^31P NMR研究（Ⅱ）

应用原位核磁波谱技术，在反应温度１４０－１４５℃，压力０．５ＭＰａ，氘代苯为溶剂，二叔丁基过氧化物为引发剂的条件下，考察了９膦双环壬烷与不同碳数直链单烯烃反应的原位＾３１Ｐ ＮＭＲ谱。实验结果表明，产产物均为烷基－９－膦环环壬烷Ｃ８ Ｈ１４ ＰＣｎＨ２ｎ＋１，但反应速度随烯烃碳数的增加而下降。     

硫醇-烯/炔点击化学制备有机/无机杂化材料

有机/无机杂化材料因其独特、优异的结构和性能已经成为目前材料领域的研究热点,硫醇-烯/炔点击化学是近年发展起来的一类新型点击化学,以其反应条件温和、速率快、产率高、产物容易分离以及高度选择性等优点受到国内外研究者的广泛关注。本文综述了近年来硫醇-烯/炔点击化学制备有机/无机杂化材料的研究进展,重点介绍了利用硫醇-烯/炔点击化学制备硅类、碳类、金属及金属氧化物类有机/无机杂化材料,并归纳了这些有机/无机杂化材料在生物医用、环境保护、光电材料等方面的应用,最后展望了硫醇-烯/炔点击化学制备有机/无机杂化材料未来的发展方向。     

有机磷化合物的研究 VIII. 酸性有机磷化合物的气相色谱

Acidic organophosphorus compounds may be identified by GLC via their methyl esters, usually prepared from diazomethane. The wide applications of this mthod are, however, limited by the toxicity of diazomethane. Tetramethyl ammonium hydroxide in methanol solution reacted rapidly with acidic organophosphorus compounds at room temperature to form tetramethyl ammonium salts, which were then converted to the corresponding methyl esters by pyrolysis at 300-350 deg.C. A simple and convenient method for separation and identification of various types of acidic phosphates, phosphonates and phosphinates by GLC has been developed. The GLC behaviours of phosphoric acid dialkyl esters, mono-esters of phenyl-and cyclohexyl-phosphonic acids as well as dialkylphosphinic acids can be represented by corrected retention time (t'R) which correlates linearly with the number of carbon atoms of the alkyl groups in these organophosphorus compounds. The influence of number of carbon atoms and isomerization of alkyl group on t'R values and retention index (I) calculated by Kovats equation was discussed. As shown by our experiments the change in retention index (ΔI) in the homologous series of phosphoric acid dialkyl esters is nearly a constant on lengthening the alkyl group of the esters with methylene linkages.     

PdCl2催化炔酸烯丙酯环化反应的密度泛函研究

用密度泛函方法(DFT)研究了PdCl2催化炔酸烯丙酯环化反应的机理. 在B3LYP/6-311G**水平上优化了各反应中间体和过渡态的结构. 计算结果表明, 反应是放热的, 主要经历了炔键的卤钯化、烯烃对烯基钯的迁移插入以及β-杂原子消除等过程. 烯烃的迁移插入是反应的手性决定步骤, β-杂原子消除是反应的速率控制步骤. 理论预测的主要产物是与实验吻合的(Z,R)-α-亚烷基-γ-丁内酯.     

Hydroboration of Phosphaalkynes by HB(C6F5)2

The hydroboration of phosphaalkynes with Piers’ borane (HB(C₆F₅)₂) generated unusual phosphaalkenylboranes [RCH=PB(C₆F₅)₂]₂ that persisted as dimers in both solution and the solid state. These P₂B₂ heterocycles underwent ring opening when subjected to nucleophiles, such as pyridine and tert‐butylisocyanide, to yield monomeric phosphaalkenylborane adducts RCH=PB(C₆F₅)₂(L). DFT calculations were performed to probe the nature of the interaction of phosphaalkynes with boranes.     

Chemistry of Several Sterically Bulky Molecules with P=P,P=C,and C≡P Bond

Several sterically protected, low-coordinate organophosphorus compounds with P=P, P=C, and C≡P bond are described in this study. Molecules such as diphosphenes, phosphaalkenes, 1-phosphaallenes, 1,3-diphosphaallenes, 3,4-diphosphinidenecyclobutenes, and phosphaalkynes are stabilized with an extremely bulky 2,4,6-tri-t-butylphenyl (Mes*) group. The synthesis, structures, physical, and chemical properties of these molecules are discussed, together with some successful applications in catalytic organic reactions.     

Silylenes and disilenes: examples of low coordinated silicon compounds

This report summarises some aspects of silicon compounds of coordination numbers two and three. As examples for such molecules, generation and trapping reactions of the sterically encumbered silylenes: dimesitylsilylene, di-tert-butylsilylene, and diadamantylsilylene are discussed. Some more recent results from the chemistry of stable and marginally stable disilenes are also considered.     

A concise review of mass spectrometry imaging

Mass spectrometric imaging allows the investigation of the spatial distribution of molecules at complex surfaces. The combination of molecular speciation with local analysis renders a chemical microscope that can be used for the direct biomolecular characterization of histological tissue surfaces. MS based imaging advantageously allows label-free detection and mapping of a wide-range of biological compounds whose presence or absence can be the direct result of disease pathology. Successful detection of the analytes of interest at the desired spatial resolution requires careful attention to several steps in the mass spectrometry imaging protocol. This review will describe and discuss a selected number of crucial developments in ionization, instrumentation, and application of this innovative technology. The focus of this review is on the latest developments in imaging MS. Selected biological applications are employed to illustrate some of the novel features discussed. Two commonly used MS imaging techniques, secondary ion mass spectrometric (SIMS) imaging and matrix-assisted laser desorption ionization (MALDI) mass spectrometric imaging, center this review. New instrumental developments are discussed that extend spatial resolution, mass resolving power, mass accuracy, tandem-MS capabilities, and offer new gas-phase separation capabilities for both imaging techniques. It will be shown how the success of MS imaging is crucially dependent on sample preparation protocols as they dictate the nature and mass range of detected biomolecules that can be imaged. Finally, developments in data analysis strategies for large imaging datasets will be briefly discussed.     

Structure of organophosphorus compounds

Journal of Structural Chemistry -