芳基金属络合物的自由基反应研究进展

综述了近年来芳基金属络合物与自由基的加成和取代反应的研究进展，并简要 讨论了该领域的发展方向。     

金—硫脲络合物成键及结构性能的研究

通过实验合成了金一硫脲络合物,测定了它的红外与紫外光谱,并用cNDO/2法进行了计算。由波谱测试及量化计算的结果分析,确定了金一硫脲络合物的结构为平面直线型分子。Au—S间的键合是强极性的σ—配位键。     

Cu（Ⅱ）—正胺络合物共价性的ESR研究

本文研究了乙胺等四种正胺配体与Cu(ClO_4)_2的配位络合物溶液的低温(77K)ESR谱。用超精细耦合常数和g值计算了σ键强度以及配位场分裂能次序。结果表明:σ键强度随着配位胺分子碳链增长而增强,至正戊胺配位络合物开始减弱;在这些Cu(Ⅱ)-正胺络合物中氨基以与氨不同的键性和Cu(Ⅱ)离子键合。     

仿生催化剂——Salen金属络合物催化不对称环氧化烯烃的基础

Salen与卟啉、Salen金属络合物与卟啉铁的结构和性质相似, 因此可将Salen金属(Salen-M)络合物认为是仿生催化剂, 它们的仿生性突出表现在不对称催化反应中的高对映异构选择性. 重点介绍了Salen-M络合物催化环氧化烯烃的反应机理, 环氧化合物的对映选择性与Salen配位体中的取代基效应(以取代常数σ_p表示)之间呈线性关系. 另外, 对映异构选择性的高低还与催化剂配体和底物的结构以及反应条件有关.     

4′-取代苯并-15-冠-5-苦味酸分子络合物的核磁共振研究

研究了15种4＇-取代苯并-15-冠-5及其与苦味酸所形成的电荷转移络合物的~1H NMR,测定了其中12种络合物的络合常数。络合常数、参考线REL～[D]的斜率以及络合前后4＇-取代苯并-15-冠-5各类质子与笨并-15-冠-5相应的质子化学位移之差△σ均与Hammett取代基常数[σ_p σ_m]呈线性关系。根据取代基对各类质子化学位移变化的影响,讨论了有关化合物的结构与性能的关系。     

多层三明治型四吡咯基金属配合物的研究进展

受合成方法的制约,对于三明治型四吡咯基金属配合物的研究长期局限于相应的双层及三层化合物。自2010年以来,通过将中性态双层稀土配合物与二价镉离子在一定条件下聚合,成功得到四层,五层和六层四吡咯金属化合物。本文从合成方法、晶体结构、单分子磁体性质及三阶非线性光学性质等方面,对这一类新型的多层三明治型四吡咯基金属配合物的研究进展进行了总结,并期待它们在新型分子功能材料研究领域包括磁光、磁手和光电复合功能分子材料方面取得令人鼓舞的新进展。     

[Nd(SSCNH_2)_4]~-的电子结构——一种有机硫配位镧系络合物的模型阴离子(英文)

本文详细研究了络阴离子{Nd[SSCN(C_2H_5)_2]_4}~-的简化模型[Nd(SSCNH_2)_4]~-的电子结构和化学键合情况。从对键能的贡献看,钕和硫原子之间的结合主要是离子性的,但从电荷的重新分布看,应该认为共价结合对成键有一定贡献。σ键起主要作用,对Nd—S和Nd—S′键来说,π键级只有σ键级的1/5～1/6。根据计算结果分析了为什么至今只合成了很少几种有机硫配位镧系络合物而存在大量稳定无机复合镧系硫化物的原因。建议了几种合成稳定的有机硫配位镧系络合物的可能途径。     

[Nd(SSCNH2)4]-的电子结构 一种有机硫配位镧系络合物的模型阴离子

本文详细研究了络阴离子{Nd[SSCN(C_2H_5)_2]_4}~-的简化模型[Nd(SSCNH_2)_4]~-的电子结构和化学键合情况。从对键能的贡献看, 钕和硫原子之间的结合主要是离子性的, 但从电荷的重新分布看,应该认为共价结合对成键有一定贡献。σ键起主要作用, 对Nd—S和Nd—S′键来说, π键级只有σ键级的1/5～1/6。根据计算结果分析了为什么至今只合成了很少几种有机硫配位镧系络合物而存在大量稳定无机复合镧系硫化物的原因。建议了几种合成稳定的有机硫配位镧系络合物的可能途径。     

4'-取代苯并-15-冠-5-苦味酸分子络合物的核磁共振研究

研究了15种4'-取代苯并-15-冠-5-及其与苦味酸所形成的电荷转移络合物的~1HNMR,测定了其中12种络合物的络合常数.络合常数,参考线RFL-[D]的斜率以及络合物前后4'-取代苯并-15-冠-5-各类质子与苯并-15-冠-5-相应的质子化学位移之差△δ均与Hammett取代基常数[σ~p+σ~m]呈线性关系.根据取代基对各类质子化学位移变化的影响.讨论了有关化合物的结构与性能的关系.     

取代环戊二烯基钕、钆、镱络合物的合成

本文合成了一些[M(THF)_2][L_2LnCl_2]络合物,其中Ln为Nd,Gd或Yb;L为C_5Me_5,C_5Me_4C_2H_5或C_5Me_4C_3H_7;M为Li或K。并分离了中性络合物(C_5Me_4C_3H_7)_2NdCl。这些络合物对空气和水非常敏感,除了含K的阴离子型络合物外,其它络合物都易溶于汽油,苯和甲苯等非极性溶剂。络合物均经元素分析、红外和核磁鉴定。     

手性席夫碱配合物用于催化不对称环氧化

手性席夫碱过渡金属配合物可以高效催化烯烃不对称环氧化反应,因此其合成及催化性能研究一直以来受到广泛的关注.本文较详细地综述了最近十年来合成的手性席夫碱过渡金属配合物及其对烯烃环氧化反应的催化性能的研究进展.重点讨论了新型的对称和非对称salen型配体过渡金属配合物的合成及其应用,分析探讨了手性席夫碱过渡金属配合物作为催化剂的优缺点、催化机理和未来发展方向.     

过渡金属络合物在精细有机合成中的应用

过渡金属化学已发展成为有机合成的重要方法,本文综述了它在精细有机合成中应用的一些进展。叙述了金属有机化合物作为亲电体与亲核试剂反应,金属有机化合物作为亲核体与亲电试剂反应,以及偶合和环化反应。应用这些反应可以巧妙地合成若干天然产物。     

Metallocomplexes of fluoroquinolonecarboxylic acids

The survey reviews the data on the synthesis, structure and biological activity of fluoroquinolonecarboxylic acids metal chelates. The influence of metal and ligand nature as well as conditions of the synthesis on the polyhedron type is discussed. The data on interaction between fluoroquinolone metal complexes and DNA are explored.     

水溶性氮杂环卡宾金属配合物的研究进展

氮杂环卡宾(NHCs)金属配合物作为一类重要的催化剂一直是有机合成领域研究的热点。近年来,通过引入水溶性配体而得到的水溶性氮杂环卡宾过渡金属配合物受到广大科研工作者的青睐。本文主要总结了水溶性NHCs的分类、合成及其在C-C偶联反应、复分解反应以及催化加氢反应中的应用,并对水溶性NHCs金属配合物的发展趋势进行了展望。     

CRYPTATES XIX. Ligands polyaza-polyoxa-macrobicycliques: Synthèse et complexes métalliques

Polyaza-polyoxa macrobicyclic ligands: its synthesis and metal complexes. The synthesis of the polyaza-polyoxa macrobicyclic ligands 1–4 is described. They form complexes with a variety of metal cations, transition metal cations as well as alkali and alkaline-earth cations. These complexes may be formulated as cation inclusion complexes, cryptates, in which the cation is contained in the intramolecular cavity. The properties of the complexes are described. An especially interesting feature is that these ligands, polymines of macrobicyclic topology, provide a means of trapping transition metal cations inside a molecular cavity; thus they impose coordination geometries and may modify the spectral and redox properties of the cations.     

Synthetic and structural chemistry of groups 11 and 12 metal complexes of the zwitterionic ammonium thiolate ligands

The chemistry of metal complexes of the zwitterionic ammonium thiolates has expanded dramatically in the recent years. This review is intended to summarize the synthesis and crystal structures of groups 11 and 12 metal zwitterionic ammonium thiolate complexes. Seven methods for the synthesis of these metal complexes of the zwitterionic ammonium thiolates are outlined: proton transfer reaction, precursor reaction, ligand exchange reaction, oxidation–reduction reaction, solid-state reaction, electrochemical reaction and hydro(solvo)thermal reaction. These metal complexes of the zwitterionic ammonium thiolates are classified according to the number of metal atoms; their specific structures are briefly discussed.     

廉价金属配合物催化的C-C与C-N键构建研究进展

综述了廉价金属铁、钴、锰等配合物催化的C-C与C-N键构建的研究进展。廉价金属配合物在催化反应中表现出不亚于贵金属配合物的催化活性,而且具有价格低廉、无毒等优点,因此成为近年来研究的热点。本文主要从廉价金属配合物催化的C-C键与C-N键的合成等方面进行总结,为今后廉价金属配合物的研究提供参考。     

Photoactive Nickel Complexes in Cross-Coupling Catalysis

Transition metal catalyzed cross-coupling reactions are important in chemical synthesis for the formation of C−C and C-heteroatom bonds. Suitable catalysts are frequently based on palladium or nickel, and lately the cheaper and more abundant first-row transition metal element has been much in focus. The combination of nickel catalysis with photoredox chemistry has opened new synthetic possibilities, and in some cases electronically excited states of nickel complexes play a key role. This is a remarkable finding, because photo-excited metal complexes are underexplored in the context of organic bond-forming reactions, and because the photophysics and the photochemistry of first-row transition metal complexes are underdeveloped in comparison with their precious metal-based congeners. Consequently, there is much potential for innovation at the interface of synthetic-organic and physical-inorganic chemistry. This Minireview highlights recent key findings in light-driven nickel catalysis and identifies essential concepts for the exploitation of photoactive nickel complexes in organic synthesis.     

The interactions of metal ions with nonsteroidal anti-inflammatory drugs (oxicams)

Much work has been focused on interactions of metal ions with nonsteroidal anti-inflammatory drugs (oxicams). Numerous attempts to synthesize several metal complexes have been published. This review highlights the synthesis and properties of the synthesized metal complexes. Different physico-chemical methods (IR, UV–Vis, measurement, thermal analysis, and NMR spectroscopy) as well as the bioactivity of the metal compounds are mentioned.     

Recent advances in the synthesis,structural diversity,and applications of mesoionic 1,2,3-triazol-5-ylidene metal complexes

Beyond the classic N-heterocyclic carbenes (NHCs) there is a subclass of NHCs called mesoionic carbenes (MICs). This review focuses on recent advances in the area of 1,2,3-triazol-5-ylidenes as the most abundant class of MICs and their metal complexes. The study of mesoionic 1,2,4- and 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene transition metal complexes is a research area with a history of just ～10 years. During this relatively short period, hundreds of these complexes have appeared in the literature, reflecting their high stability and simpler synthesis compared with NHCs. Specifically, this review is focused on advances in the synthesis of 1,2,3-triazol-5-ylidene metal complexes derived from palladium, silver, gold, ruthenium, iridium, rhodium, iron, molybdenum, cobalt, nickel, platinum, and osmium, together with their catalytic, medicinal, and photophysical applications.