聚-4-氧杂-6,7-双二苯膦基庚基硅氧烷铑配合物的合成及其催化硅氢化性能

4-氧杂-6,7-二氯庚基三甲氧基硅烷依次与二苯膦钾、气相法二氧化硅、三氯化铑作用,合成了聚-4-氧杂-6,7-双二苯膦基庚基硅氧烷铑配合物。它对烯烃与取代烯烃的硅氢化反应具有良好的催化活性。     

桥联环戊二烯金刚烷氨基二甲基钛配合物的合成及其催化丙烯聚合

合成了新型限制几何构型四甲基环戊二烯金刚烷氨基二甲基钛配合物(1-Adamantyl)NSiMe₂(C₅Me₄)]TiMe₂(c)。 通过¹H NMR、元素分析以及单晶衍射分析等技术手段确定了该配合物的结构。 与其叔丁基氨配合物tBuNSiMe₂(C₅Me₄)]TiMe₂(a)对比,在修饰甲基铝氧烷(MMAO)/2,6-二叔丁基-4-甲基苯酚(BHT)活化下进行丙烯聚合,探讨了氨基配体结构及聚合条件对聚合性能的影响。 在保持准活性聚合的条件下,金刚烷胺基配合物c的催化活性为562 kg_(PP)/(mol_(Ti)·h),为叔丁胺基配合物a的2倍以上,说明金刚烷胺的引入有助于提高体系的链增长速率。     

杂元素冠醚的研究（Ⅵ）──7，11－二硒杂苯并－13－冠－4铂配合物的合成及其催化硅氢化性能

合成了７，１１－二硒杂苯并－１３－冠－４及其铂配合物，并从底物的性质、反应温度、催化剂用量以及化学气氛四个方面考察了该配合物对烯烃与三乙氧基硅烷的硅氢加成反应的催化特性。与单硒杂冠醚配合物相比，该配合物对某些烯烃的催化活性较高，但催化反应需要的温度也较高．     

有机硅聚合物负载环硫乙烷铂配合物的合成与催化性能

<正> 有机硅聚合物负载硫醚与铂的配合物可作为烯烃硅氢加成的有效催化剂,但其中部分配合物的回收再用性能不太理想,合成亦比较繁琐。考虑到环硫乙烷中硫原子的未共用电子对远比一般硫醚中硫原子的未共用电子对更加暴露,有可能与过渡金属形成更稳定的配合物,从而减少催化过程中金属的流失,我们合成了气相法二氧化硅固载的聚-4-氧杂-6,7-环硫庚基硅氧烷铂配合物,研究了该配合物对烯烃硅氢加成反应的催化性能。本文报道所得到的一些结果。     

CONFIGURATION OF VO(OR)_2Cl-Al(i-Bu)_3 CATALYST SYSTEM AND CHARGE DISTRIBUTION OF VANADIUM CENTRAL ION

According to the caiculation of quantum chemistry it come be deduced that conngurauons or the catalysts VO(OR)_2Cl-Al (i-Bu)_3, for the alternating Copolymerization of butadiene with propene, the highest reactive configuration was A. When the catalyst complex forms the configuration A, the energy of the system was the lowest; the central vanadium atom had relatively high positive charge and whose frontier orbital overlapped easily with the frontier orbital of butadiene to form coordination complex, so it was concluded from the experimental results and calculations that the configuration of the catalyst of relatively high activity was A.     

纳米2,4-二羟基苯甲酸铅(Ⅱ)配合物的合成及其燃烧催化性能研究

采用液相分散沉淀法制备了纳米2,4-二羟基苯甲酸-Pb(Ⅱ)配合物粉体,并用TG,XRD,TEM,IR和元素分析对产物进行了表征.研究了反应条件对产物粒径和粒子形貌的影响.用DSC考察了产物对吸收药热分解的催化作用.结果表明,在水溶液中得到的产物为15nm×40nm的棒状粒子,而在乙醇溶液中得到的是粒径约为50nm的球形粒子.产物对吸收药热分解有显著的催化效果,使吸收药的分解峰温降低5.6℃,分解热增加918J/g.     

高分子载体四氯化锡复合物催化剂(Ⅱ)——苯乙烯、甲基丙烯酸甲酯共聚物-四氯化锡复合物

高分子载体催化剂的研究和开发日益受到重视。四氯化锡是一种常用的强Iewis酸,在空气中强烈水解而产生大量盐酸烟雾,保存和使用都不方便,我们曾将四氯化锡与聚苯乙烯交联白球反应制成了一种高分子载体催化剂,对酯化、缩醛、缩酮等有机反应有良好的催化性能,但它在反应中洗脱流失严重,重复使用性能很差,基本上是十种高分子保护型的载体催化剂。为了改善其稳定性,从而提高重复使用性能,我们合成了含有富电子基团的新高分子载体,使四氯化锡与载体中的富电子基团形成较稳定的复合物,使之既保持良好的催     

1H-NMR and UV studies of Rh complexes as a stereoregular polymerization catalysts for phenylacetylenes: Effects of ligands and solvents on its catalyst activity

Phenylacetylene and its homologues bearing methoxy or chloro groups in the para position of the phenyl ring were stereoregularly polymerized by Rh complex catalysts, e.g., [Rh (norbornadiene) Cl]₂, in the presence of various solvents. The ¹H-NMR and UV study of the Rh complex showed that the activity of the Rh catalysts greatly depends upon not only the ligand in the Rh catalyst but also on the solvent used, e.g., polyphenylacetylene with a highly cis-transoidal content was quantitatively obtained when norbornadiene was coordinated as the ligand, and triethylamine (TEA) was used as solvent, whereas tetrahydrofuran (THF) and benzene reduced the cis content. It was also found that the Rh catalyst as a dimer complex dissociates into the monomeric species not only when TEA was used but also when alcohol, benzene, and THF were used. The resulting monomeric species was considered as the important propagation species in this polymerization. The sharp line width observed in the ¹H-NMR spectrum of polyphenylacetylene and its homologues which were prepared in ethanol or TEA was interpreted by the narrow chemical shift distribution arising from the high cis content. © 1994 John Wiley & Sons, Inc.     

Tetrahydrosalen backboned gadolinium complex as initiator for the ring-opening polymerization of ε-caprolactone

Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through salt metathesis. This complex was successfully used to initiate the ring-opening polymerization of ε-caprolactone. The initiation conditions in different temperature, monomer-to-initiator ratio and time were investigated. Under the condition: [ε-caprolactone]: [catalyst]=600,56℃, toluene: 2ml, poly(ε-caprolactone) (PCL) with Mw=11,2782 and PDI=1.96 was achieved.     

Four-component coupling reactions of silylacetylenes, allyl carbonates, and trimethylsilyl azide catalyzed by a Pd(0)-Cu(I) bimetallic catalyst. Fully substituted triazole synthesis from seemingly internal alkynes

Fully substituted triazoles were synthesized via the four-component coupling reaction of unactivated silylacetylenes, two equivalents of allyl carbonates, and trimethylsilyl azide in the presence of a Pd(0)-Cu(I) bimetallic catalyst. Various trisubstituted 1,2,3-triazoles were obtained in good yields. The reaction most probably proceeds through the [3+2] cycloaddition reaction between the alkynylcopper species and azide followed by the cross-coupling reaction between the vinylcopper intermediate and π-allylpalladium complex.     

聚苯乙烯负载碲醚铂,铑配位硅氢化催化剂

本文报道首例高分子负载碲铂配位硅氢化催化剂。氯甲基化交联聚苯乙烯在氢化钠存在下，在二氧六环中与民β,β'-二羟乙基碲醚缩合，再与氯亚铂酸钾或三氯化铑反应，得到相应的聚苯乙烯负载碲醚铂、铑配位硅氢化催化剂，二者对烯烃与三乙氧基硅烷的硅氢化反应具有良好的催化活性。     

Supported dichlorobis(3-hydroxi-2-methyl-4-pyrone)Ti(IV) catalysts: Evaluation on ethylene polymerization

Dichlorobis(3-hydroxi-2-methyl-4-pyrone)Ti(IV) complex was grafted on different inorganic supports, namely different kinds of SiO₂, MAO-modified silica, MCM-41, Al₂O₃, ZrO₂ and MgO. The resulting supported catalysts were shown to be active in ethylene polymerization using methylaluminoxane (MAO) as cocatalyst, most of them being even more active that the homogeneous complex. The highest catalyst activities were observed for the Ti complex supported on SiO₂ 948 activated at 450 °C, MCM-41 and Al₂O₃.     

单层型氧化铁催化剂的制备及其前体的表征:Ⅱ.催化剂前体的表征

用三种方法，即草酸络铁（Ⅱ）酸铵的过量水溶液含浸，三乙酰丙酮铁的甲苯溶液热吸附和硝酸铁溶液饱和浸渍法制备了种载体上氧化铁的负载样品，对用不同方法制备的催化剂前体中表面铁物种的存在形式，结构和分散度等进行了细致的表征和详细的讨论，并与焙烧后样品中Ｆｅ＾３＋的最终形态进行了关联。     

Microwave-Assisted Catalytic Acetylation of Alcohols by Gold-Nanoparticle–Supported Gadolinium Complex

A gold nanoparticle (AuNP)–supported gadolinium complex (RS-Au-L-Gd) catalyst was prepared through simple chelation of GdCl₃ to the surface-bound spacer, 1,4,7-tris(carboxymethyl)-10-(11-mercaptoundecyl)-1,4,7,10-tetraazacyclododecane (HSDO3A). This AuNP-supported Gd complex was found to be a highly effective catalyst for the acetylation of various alcohols and phenol in the presence of acetic anhydride. With a loading of 0.4 mol% of RS-Au-L-Gd, the almost complete transformation can be achieved in 60 s under microwave irradiation conditions. This hybrid catalyst was air stable, water soluble, dissolvable in many organic media, and precipitable. It can be readily recycled more than eight times without any significant loss of its catalytic activity.     

聚烯烃催化剂的发展及我们的对策

评述了聚烯烃催化剂的几个重要发展阶段，讨论了Ziegler-Natta催化剂，茂金属催化剂及非茂有机金属催化剂的组成及特征，提出了我国在聚烯烃催化剂开发方面的对策。     

聚γ-(m-二苯膦苯基)丙基硅氧烷——铂络合物对烯烃硅氢化反应的催化特征

本文报道二氧化硅负载的三苯膦铂络合物——聚γ-(m-二苯膦苯基)丙基硅氧烷铂络合物对三甲氧基硅烷与不饱和化合物进行硅氢加成反应的催化特性.在底物用量的万分之一摩尔量的铂络合物存在下,1-己烯、1-癸烯、1-十二碳烯、苯基烯丙醚和ω-氯代十一碳烯在60或40℃平稳地与三甲氧基硅烷发生硅氢加成反应,唯一地得到末端加成产物,产率均在85％以上.其催化活性在反应初期低于四(三苯膦)合铂,但后期反应速度和硅氢化产率均较高.实验表明,聚γ-(m-二苯膦苯基)丙基硅氧烷与四(三苯膦)合铂反应制得的铂络合物(1)比与氯铂酸反应制得的铂络合物(Ⅱ)催化活性高.其次,反应气氛对硅氢加成反应具有决定性的影响.在空气气氛中,硅氢化反应平稳地进行;在氮气气氛中,不发生反应.     

A novel fumed silica-supported nitrogenous platinum complex as a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane

A novel fumed silica-supported nitrogenous platinum complex was conveniently prepared from cheap γ-aminopropyltriethoxysilane via immobilization on fumed silica in toluene, followed by a reaction with hexachloroplatinic acid. The title complex was characterized by fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It was found that the complex is an efficient and stable catalyst for the hydrosilylation of olefins with triethoxysilane. The title platinum complex could be separated by simple filtration and reused several times without any appreciable loss in the catalytic activity.     

稀土席夫碱配合物催化己内酯可控开环聚合

 通过稀土氯化物与席夫碱钠盐的交换反应制备了一系列以 3,5-二叔丁基水杨醛缩苯胺为配体的稀土席夫碱配合物. 对其中的钕席夫碱配合物进行了 X射线单晶衍射分析, 发现其单晶结构为五角双锥构型, 所得席夫碱稀土配合物可以单组分催化 ?-己内酯开环聚合. 深入研究了钕席夫碱配合物催化己内酯的开环聚合机理, 考察了不同聚合条件对单体转化率、产物分子量及分子量分布的影响. 结果表明, 该聚合反应速率为一级, 聚合反应具有较好的可控性. 聚合物端基分析表明, 聚合反应以配位-插入机理进行.     

含能配合物[Pb(AZTZ)(bpy)(H2O)·2H2O]n合成、结构及燃烧催化性能

设计合成了含能配合物[Pb(AZTZ)(bpy)(H2O)·2H2O]n(1)(AZTZ=5,5’-偶氮四唑阴离子, bpy=2,2’-联吡啶), 用X射线单晶衍射法测定了其分子结构. 该晶体属三斜晶系, P1空间群, a=0.7341(6) nm, b=1.0050(8) nm, c=1.3367(1) nm, α=95.354(1)°, β=101.450(1)°, γ=101.233(1)°, V=0.8927(1) nm3, Z=2, S=1.030. 利用元素分析、红外光谱以及热重分析等手段对标题化合物进行了表征, 并研究了配合物(1)对固体双基推进剂的燃烧催化作用. 结果表明, 配合物(1)可以有效地提高固体双基推进剂的燃速.     

Hybrid organic-inorganic silica materials containing di(2-pyridyl)methylamine-palladium dichloride complex as recyclable catalysts for Suzuki cross-coupling reactions

High surface hybrid silica materials containing di(2-pyridyl)methylamine-palladium dichloride complex covalently bonded to the silica matrix were prepared by sol-gel process and successfully tested as reusable catalysts for Suzuki cross-coupling reactions.