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烷氧桥相连的四苯基双金属卟啉配合物的红外光谱研究 总被引:1,自引:1,他引:1
研究了烷氧桥相连的四苯基双卟啉及其Mn(Ⅱ),Fe(Ⅲ),Co(Ⅱ)配合物的红外光谱(3600~150cm^-1),对一些主要吸收谱带进行了经验归属,金属敏感谱带出现1558.2(以H2P-H2P为例)、1477.2,1401.9,1350.5,1001.7,965.9,877.3和798.8cm^-1附近,金属和烷氧桥都敏感的谱带出现在1595.1(以H2P为例)、1491.1,851.1和72 相似文献
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某些人工合成的金属卟啉,由于其活化分子氧的功能,被广泛用作生物模拟氧化反应中的催化剂。金属四苯基卟啉及其衍生物是用得最普遍的模型化合物。文献中巳报道过各种四苯基卟啉衍生物的合成方法,但尚未见带烷硫基的四苯基卟啉衍生物的系统合成方法。本文报道这类四苯基卟啉衍生物及其金属配合物的合成。 本文采用通常的一步法合成四苯基卟啉衍生物,即首先参照文献方法合成烷硫基苯甲 相似文献
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单取代色氨酸四苯基卟啉及其配合物的合成、结构表征及催化性质研究 总被引:6,自引:1,他引:6
模拟细胞色素 P- 4 5 0的活性中心金属卟啉及周围氨基酸残基的结构 ,研究以其共轭大 π电子体系和中心金属原子价改变为基础的金属卟啉的氧化还原性质 ,以及中心金属对轴向配体的配位能力是当前人们感兴趣的课题[1 ] 。本文报道了 5 - [(对 - N-色氨酸丁氧基 )苯基 ]- 10 -15 - 2 0 -三 (对氯苯基 )卟啉及其铁、钴、锰配合物的合成、结构表征和对芳醛的催化氧化行为。实 验 部 分合成1.色氨酸四苯基卟啉 (H2 L )的合成 : 按文献 [2 ]先合成单对羟基卟啉 (收率 4 .2 % ) ,再与1,4二溴丁烷反应得单对溴丁氧基四苯基卟啉 (收率 6 0 % ) ,… 相似文献
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过渡金属离子为模板的卟啉过渡金属配合物的合成研究 总被引:3,自引:0,他引:3
系统研究了以过渡金属离子为模板的卟啉配合物的合成方法,探讨了金属离子加入的时间、加入方式,溶剂各组分配比,反应温度,反应时间等因素对反应的影响,得到最佳工艺参数:金属盐的加入最好在加入芳香醛和吡咯10~15min后,反应混合液的温度降到90℃以下,加入醋酸盐;混合溶剂配比为(2~5)∶(1~4)∶1;反应温度为120~145℃;反应时间为40~80min。并且利用该方法合成了34种金属卟啉配合物。利用元素分析,UV-Vis,IR, 1H NMR对金属卟啉配合物的结构进行了表征,利用TG-DTA研究了它们的热稳定性,利用EPR研究了它们的顺磁性。结果表明:该方法操作简便,产物易于分离、提纯,产率由原来两步合成法的10%~25%提高到35.1%~48%。 相似文献
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Reaction of [Mn(bpm)2]2+ with K3[Co(CN)5(NO)] produces a cyano-bridged bimetallic compound,{[Mn(bpm)2]1.5[Co(CN)5(NO)]}·2H2O (1), (bpm=bis(1-pyrazol)methane). Compound 1 crystallizes in the tetragonal space group P43212 with a=1.305 08(8) nm, b=1.305 08(8) nm, c=4.386 7(5) nm, V=7.471 5(10) nm3, and Z=8. Complex 1 exhibited a structure of a pentanuclear cluster. The Mn2+ ions each are surrounded by bpm ligands, forming the [Mn(bpm)2]2+ cation fragment. Three cation fragments are connected to the two anion fragments, [Co(CN)5(NO)]3-, by cyanide bridges. The five metal ions form a trigonal bipyramidal structure, where the Mn2+ ions are situated in the equatorial plane and the Co2+ ions are on both sides of the plane. As a semirigid ligand, bpm is more flexible than rigid 2,2′-bipydine, and it results in the two different configurations in the [Mn(bpm)2]2+ cation fragment. CCDC: 635764. 相似文献
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两个单桥连的双环戊二烯(C5Me4H)E(C5Me4H)(E=C6H4,(C6H4)2)分别与Re2(CO)10在均三甲苯中加热回流,得到了2个双核配合物(E)[(η5-C5Me4)Re(CO)3]2(E=C6H4(1),(C6H4)2(2))。通过元素分析、红外光谱、核磁共振氢谱和碳谱对配合物1和2的结构进行了表征,用X射线单晶衍射分析测定了配合物的结构。同时对2个配合物在芳香族化合物Friedel-Crafts酰基化反应中的催化活性进行了研究。 相似文献
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两个单桥连的双环戊二烯(C5Me4H) E(C5Me4H)(E=C6H4,(C6H4)2)分别与Re2(CO)10在均三甲苯中加热回流,得到了2个双核配合物(E)[(η5-C5Me4) Re(CO)3]2(E=C6H4(1),(C6H4)2(2))。通过元素分析、红外光谱、核磁共振氢谱和碳谱对配合物1和2的结构进行了表征,用X射线单晶衍射分析测定了配合物的结构。同时对2个配合物在芳香族化合物Friedel-Crafts酰基化反应中的催化活性进行了研究。 相似文献
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采用适当分子量的低软化点聚碳硅烷(LPCS)和四甲基二乙烯基二硅氮烷(TMDS)为原料,利用硅氢加成反应合成了高软化点聚碳硅烷(HPCS).研究了该反应的过程与特点,探讨了TMDS加入比例对产物特性的影响及其结构变化与可纺性的关系.结果表明,反应初期首先形成含乙烯基侧基的悬挂式结构,并随着硅氢加成反应完成,在LPCS分子间形成Si—N—Si桥联式结构.通过控制TMDS的加入比例,可以调控桥联反应程度从而控制产物的分子量及软化点.控制TMDS/LPCS质量比为0.08,得到了软化点为244~278℃,Mn=2.5×103,分子量呈双峰分布且具有良好可纺性的聚碳硅烷,适用于制备高性能连续Si C纤维. 相似文献
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氨基二硫代甲酸酯类化合物的合成新方法 总被引:7,自引:0,他引:7
在无水磷酸钾存在下,伯胺、仲胺和哌嗪与二硫化碳和不同的卤代烃于室温反应,高收率的生成对应的氨基二硫代甲酸酯.胺和卤代烃中含有-CONR2,-OH,-CO2H,-NO2,-CO2R,-CH(OR)2,-C=C-,-CH2OR,呋喃环和糖环等对酸或碱敏感的基团不受影响. 相似文献
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《Analytical letters》2012,45(11):1809-1824
Abstract The features of combining a chemically modified electrode (CME) with an artificial receptor system, prepared by imprinting electropolymerized [Ni (Protoporphyrin IX) dimethyl ester] [Ni-(PPIX)] in the presence of nitrobenzene, were studied. The responses of the modified glassy carbon electrode towards template molecules were analyzed by cycling over the nitrobenzene reduction wave. The specific signal was much higher than the non-specific one which demonstrates the selectivity of such a system. This approach has potential for preparation of selective polymeric films on the surface of different transducers. 相似文献
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Wenxiu Lv Maosheng Li Youhua Tao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(19):e202402541
Nylon, a widely-used high-performance thermoplastic, boasts exceptional durability and resistance to various solvents and weak acids, making it indispensable across diverse applications. However, its nonbiodegradable nature has led to alarming environmental pollution in land and oceans. Chemical recycling to monomers (CRM) stands as a crucial strategy for establishing a circular plastic economy, but the CRM of nylon remains largely unexplored. Herein, we introduce the bridged bicyclic lactam 5-azabicyclo[2.2.1]octan-6-one (5/6-LM), evolved from δ-valerolactam and pyrrolidone, to solve the trade-off in depolymerizability and performance. Notably, 5/6-LM exhibits nearly 95 % conversion in mild polymerization conditions and efficient depolymerization catalyzed by lewis acids. This compound is synthetically accessible from commercially available chemicals in a single step at room temperature, demonstrating high efficiency and scalability up to 50 g in laboratory. Furthermore, the resulting polyamide displays remarkable attributes including high crystallinity and thermostability up to 283 °C, significantly broadening the scope of chemically recyclable nylons. 相似文献
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M. Sc. Niklas Felix König Dr. Abdelaziz Al Ouahabi Dr. Salomé Poyer Prof. Laurence Charles Dr. Jean-François Lutz 《Angewandte Chemie (International ed. in English)》2017,56(25):7297-7301
A three-step post-polymerization modification method was developed for the design of digitally encoded poly(phosphodiester)s with controllable side groups. Sequence-defined precursors were synthesized, either manually on polystyrene resins or automatically on controlled pore glass supports, using two phosphoramidite monomers containing either terminal alkynes or triisopropylsilyl (TIPS) protected alkyne side groups. Afterwards, these polymers were modified by stepwise copper-catalyzed azide–alkyne cycloaddition (CuAAC). The terminal alkynes were first reacted with a model azide compound, and after removal of the TIPS groups, the remaining alkynes were reacted with another organic azide. This simple method allows for quantitative side-chain modification, thus opening up interesting avenues for the preparation of a wide variety of digital polymers. 相似文献
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HuaRongZHAO 《中国化学快报》2002,13(5):402-404
Benzotriazole,aldehydes and primary selenoamides react together with elimination of water to form 1:1:1 adducts which are reduced smoothly by NaBH4 to give the N-substituted selenoamides in good yield. 相似文献