（dppe）Rh（μ—CO）2M（CO）3（M=Cr,Mo,W）的合成,表征和催化功能

合成和表征了（ｄｐｐｅ）（Ｒｈ（μ－ＣＯ）２Ｍ（ＣＯ３）（Ｍ＝Ｃｒ，Ｍｏ，Ｗ）异双核金属羰基化合物，考察了ＳｉＯ２负载的这组配合物催化一氧化碳氢化反应和丙烯氢甲酰化反应的活性和性，记录了催化生氧化碳氢化反应的原位ＦＴ－ＩＲ谱。     

（dppe）Rh（μ－CO）_2M（CO）_3（M＝Cr、Mo、W）的合成，表征和催化功能

合成和表征了（ｄｐｐｅ）Ｒｈ（μ－ＣＯ）２Ｍ（ＣＯ）３（Ｍ＝Ｃｒ、Ｍｏ、Ｗ）异双核金属羰基化合物。考察了ＳｉＯ２负载的这组配合物催化一氧化碳氢化反应和丙烯氢甲酰化反应的活性和选择性。记录了催化一氧化碳氢化反应的原位ＦＴ－ＩＲ谱     

SBA-15中异双核金属配合物的结构和催化性能

合成了四个具有混合价态的大环d-f异双核配合物[M1M2L](NO3)(H2O)n(L代表配体).采用浸渍法将四个d-f异双核配合物分别固载在中孔分子筛SBA-15上制得负载催化材料.SBA-15采用微波加热法合成.IR、UV-vis、 XRD、 ICP-AES和 TG/DTA技术表征表明,异双核配合物被固载后,配合物结构仍保持完整.以环己烷氧化为探针反应, 考察了上述负载催化材料的催化性能,并分析了不同金属离子或取代基对催化剂活性及选择性的影响.同时还系统考察了溶剂、反应时间、反应温度、对环己烷氧化反应的影响.结果表明,该催化剂在环己烷氧化反应中具有较好的活性及稳定性.     

负载型Cu2（OAc）2／SiO2催化剂的制备表征及其活化——CO2和EO中成EC的TPD和Insi

用表面性性和金属嫁接相结合的双核移植法制备了SiO2负载的双核配合物催化剂Cu2(OAc)2/SiO2,用络合滴定,IR,固定相UV-Vis光谱和磁分析方法表征了催化剂表面的化学组成,桥基配体的配位方式`金属离子的价态和配位环境,根据实验结果,人出了催化剂的总体模型,并讨论了催化剂的形成机理,运用TPD和insitu-IR技术研究了催化剂对CO2和环氧乙烷(EO)的化不吸附特性及催化合成碳酸乙烯酯(EC)的反应性能,实验结果表明,CO2和EC在催化剂表面形成桥式化学吸附态,其脱附峰温度分别为120℃和130℃,催化剂对CO2和EO合成EC有良好的催化活性.     

SBA-15分子筛负载双金属配合物的合成及其催化活性

合成了SBA-15分子筛负载的同双核金属配合物{[M2LCl3]Cl/SBA-15-NH2,M=Co,Cu,Cr,H4L=二(o-亚甲基苯亚甲基三亚乙基四胺}和异双核金属配合物{[CuEuL′](NO3)(H2O)3/SBA-15-NH2,H2L′=N,N′-二(o-羟基-m-甲酰基苯甲基)哌嗪},其结构经UV,1H NMR,IR和元素分析表征。以双核金属配合物为催化剂,过氧化氢为氧化剂,催化二苯甲烷合成二苯甲酮。考察催化剂的种类、反应时间和反应温度对该反应的影响。结果表明,在70℃反应7 h的反应条件下,[Cr2LCl3]Cl/SBA-15-NH2显示了最高的催化活性,二苯甲酮产率达58.1%。     

超临界条件下CO2和丙烯直接合成甲基丙烯酸Ni2(OCH3)2/SiO2催化剂

超临界反应;负载型催化剂;双核桥联配合物;配合物;超临界条件下CO2和丙烯直接合成甲基丙烯酸Ni2(OCH3)2/SiO2催化剂     

负载型Cu2(OAc)2/SiO2催化剂的制备表征及其活化——CO2和EO合成EC的TPD和In sisu-IR研究

用表面改性和金属嫁接相结合的双核移植法制备了SiO2 负载的双核配合物催化剂Cu2 (OAc) 2 /SiO2 ,用络合滴定、IR、固定相UV Vis光谱和磁分析方法表征了催化剂表面的化学组成、桥基配体的配位方式、金属离子的价态和配位环境 .根据实验结果 ,给出了催化剂的总体模型 ,并讨论了催化剂的形成机理 .运用TPD和insitu IR技术研究了催化剂对CO2 和环氧乙烷 (EO)的化学吸附特性及催化合成碳酸乙烯酯 (EC)的反应性能 .实验结果表明 ,CO2 和EC在催化剂表面形成桥式化学吸附态 ,其脱附峰温度分别为 12 0℃和130℃ ;催化剂对CO2 和EO合成EC有良好的催化活性 .     

三乙烯四胺-咪唑的非对称异双核配合物的合成及电化学性质

许多过渡金属含氮配合物具有抗菌、抗癌、抗病毒等生物活性,受到人们的广泛重视[1]。其中三乙烯四胺(trien)是有效的生成单双核配合物的含氮配体,已设计合成了一系列过渡金属及稀土金属的均双核和异双核配合物,并进行了结构表征和性能研究[2]。对于其异双核咪唑桥联配合物,前文     

超氧化物歧化酶模型化合物的合成, 表征和活性测定

合成了二(2-苯并咪唑亚甲基)胺(N3)及其四种全新的过渡金属的双核配合物。通过元素分析、红外光谱和紫外光谱对配体及配合物进行了结构表征,利用邻苯三酚自氧化法测定了四种模拟化合物催化超氧阴离子自由基歧化反应的活性。     

二氧化碳和丙烯在Cu2(OEt)2/SiO2催化下超临界合成甲基丙烯酸

负载型双核金属乙氧基配合物催化剂Cu2(OEt)2／SiO2采用表面改性法制备。运用滴定、IR、DSC和超临界反应技术对催化剂的表面结构、化学吸附性质和反应性能进行了研究。结果表明：负载型双核金属乙氧基配合物Cu2(OEt)2／SiO2中Cu”与载体SiO2表面O^2-以双齿配位形式键合,存在Cu2(OEt)2双核结构;二氧化碳在催化剂表面吸附形式形成桥式和乙氧碳酸酯基物种两种吸附态,丙烯则只有一种分子吸附态;在超临界的反应条件下,二氧化碳和丙烯在Cu2(OEt)2／SiO2催化剂上可以高选择性地合成甲基丙烯酸;反应物分子共吸附于催化剂表面,同一活性基元以及羧酸根与丙烯解离吸附态的形成是反应顺利进行的关键因素。     

有机硅聚合物负载膦铂,膦铑络合物的合成及催化硅氢化性能

从p-氯烯丙苯出发,通过相继地与三甲氧基硅烷进行硅氢加成、二苯膦钾膦化、气相法二氧化硅固载化,再与氯亚铂酸钾或三氯化铑反应,合成了聚γ-(p-二苯膦苯基)丙基硅氧烷铂、铑络合物。两者对烯烃与三乙氧基硅烷的硅氢加成反应具有良好的催化活性。     

丙烯酸酯三元共聚物负载硫铂络合物的合成及催化性能

丁二醇二丙烯酸酯、丙烯酸甲酯、丙烯酸β-氯乙酯或丙烯酸ω-氯己酯进行三元共聚,合成了两类4种带ω-氯侧基的交联型聚丙烯酸酯.它们以乙硫醇硫醚化,再与氯亚铂酸钾反应,得到4种交联型聚丙烯酸酯负载的硫铂络合物.这些络合物对癸烯-1、十二烯-1、苯基烯丙醚、苯乙烯与三乙氧基硅烷的硅氢加成反应具有良好的催化活性.讨论了温度、催化剂用量对催化性能的影响及催化剂的重复使用情况.     

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.     

A Sterically Hindered Zirconocene Complex (1,2-Ph2C5H3)2ZrCl2:Synthesis, Structure and Properties as Olefin Polymerization Catalyst

SinceKaminskyeIal.discoveredthehighlyactivezirconocenedich1oride/methyl-aluminoxane(MAO)catalyticsystemforolefinpolymerization',intensiveresearchworkhasbeenfocusedondevelopingnewgroup4metal1ocenecatalystsforimprovingcatalystactivitiesandpolymerproperties"'.Inthedevelopmentofnewmetallocenecatalystsystems,liganddesignandmodificationhaveplayedanimportantrole.lthasbeenknownthatevenminormodificationofagivenligandframeworkcouldresultinsignificantchangesincatalystactivitiesandpolymerproperties'.Int…     

In situ FT-IR study on CO2 hydrogenation over SiO2-supported PtM (M = Cr, Mo, W) complex catalysts

The in situ FT-IR spectra were used to study the CO₂ hydrogenation reaction over the SiO₂-supported heterobinuclear metal complex catalysts, PtM (M=Cr, Mo, W). The bands, which correspond to the formate species absorbed on the catalysts, were observed. During the hydrogenation reactions, the adsorbed linear and bridging CO was not observed. The experimental results suggest that for the CO₂ and CO hydrogenation reaction over the same catalysts, their catalytic active intermediate species and the reaction mechanisms should be different.     

Electron Effect of p-Substituent on Iron（Ⅱ） and Cobalt（Ⅱ） Pyridinebisimine Catalyst for Ethylene Polymerization

A series of 2,6-bis（imino）pyridyl iron and cobalt complexes bearing p-substituent [2,6-（ArN=CMe）2C5H3N]- MCl2 （Ar=2,6-Me2C6H3, 2,4,6-Me3C6H2, 2,6-Me2-4-BrC6H2, 2,6-Me2-4-ClC6H2, 2,4-Me2-6-BrC6H2, 2,4-Me2-6- ClC6H2, while M=Fe, Co） have been synthesized and investigated as catalysts for ethylene polymerization in the presence of modified methylaluminoxane as a cocatalyst. The electron effect and positions of the substituent of pyridinebisimine ligands were observed to affect considerably catalyst activity and polymer property.     

SYNTHESIS AND CATALYTIC ACTIVITY OF PLATINUM COMPLEX OF ACRYLATE TERPOLYMER WITH Se, N BIDENTATE LIGAND

1NTRODUCTIONTheacrylateterpolymer--supPOrtedsulfideplatinumcomplexanddisulfideplatinumcomplex['--2]werestudiedinthehydrosilylationofolefins.Itisfoundthattheyhavehighcatalyticactivityandreusedproperties.LiuXFetal.[3)synthesizedselena--crowneitherplatinumcomplexesandreportedtheircatalyticactivityofhydrosilylation.Clarketal.[4)reportedthatthecatalyticactivityofPiLL'Clz(L=PPh2,L'=S,N)ishigherthanthatofPtLZC12orPtL'ZC12inhydrosilylation.Inthispaper,wereportthesynthesisofanewacrylatete…     

ONO pincer palladium (II) complexes featuring furoylhydrazone ligands: Synthesis,characterization and catalytic activity towards Suzuki–Miyaura coupling reaction

Four new palladium pincer complexes incorporating ONO type furoylhydrazone ligands have been prepared in good yields. These palladium complexes were structurally characterized by elemental analysis, infrared, ¹H‐ and ¹³C‐NMR spectra. X‐ray single crystal analyses of Pd1–Pd4 revealed that the metal center adopted a slightly distorted square planar geometry in which the hydrazone bound the metal ion via the phenolic‐O, azomethine‐N and imidolate‐O atoms. Using these ONO pincer complexes as catalyst, excellent yields of biaryls could be obtained for coupling of arylboronic acids with aryl bromides at a low catalyst loading (0.01 mol%).     

New Half-sandwich Zirconium（IV） Complexes Containing Salicylaldimine Ligands： Synthesis,Characterizations and Catalytic Properties

Two new half-sandwich zirconium（IV） complexes bearing salicylaldimine ligands of the type Cp＊Zr[2-tBu-4-R-6-（CH=NiPr）C6H2O]C12[R=H（1）, tBu（2）] were prepared by the reaction of Cp＊ZrC13 with the corresponding lithium of salicylaldimine ligands 2-tBu-4-R-6-（CH=NiPr）C6H2OLi[R=H（LiLa）, tBu（LiLb）]. Com- plexes 1 and 2 were characterized by 1H NMR, BC NMR spectroscopy and elemental analysis. When activated with AliBu3 and Ph3CB（C6F5）4, both complexes 1 and 2 exhibited reasonable catalytic activities for ethylene polymeriza- tion, producing polyethylenes with moderate molecular weight. Complexes 1 and 2 also exhibited reasonable catalyt- ic activities for ethylene copolymerization with 1-hexene, producing poly（ethylene-co-l-hexene）s with moderate molecular weight and reasonable 1-hexene content.