用茂钛配合物高效、高选择性催化4-乙烯基环己烯的异构化

The catalytic species [Cp2TiH], formed in situ from the reaction of titanocene dichloride with Grignard reagents having a β-H, was found to be a very effective catalytic system for isomerization of diolefin[1～3]. Based on our previous work[3], the titanium-catalyzed isomerization of 4-vinyl-cyclohexene (VCH) was studied in some detail. In this communication, we report the use of various substituted titanocene and polymer-supported titanocene complexes with Grignard reagents as catalyst for the isomerization of VCH. It was reported that base-catalyzed isomerization of VCH formed a very complicated mixture with 60 % conversion[4].     

含膦配体的铂羰基配合物催化苯的光羰化反应

采用“原位反应”的方法,研究了配合物Ｐｔ（ＰＭｅ３）２（ＣＯ）２和Ｐｔ（ｄｉｐｈｏｓ）（ＣＯ）２（ｄｉｐｈｏｓ：１,２－二（二特丁基膦）乙烷,即ｄ（ｔ－Ｂｕ）Ｐｅ,１,２－二（二环己基膦）乙烷,即ｄＣｙｈＰｅ;１,２－二（二环戊基膦）乙烷,即ｄＣｙｐＰｅ;１,２－二（苯基特丁基膦）乙烷,即Ｐｈ（ｔ－Ｂｕ）Ｐｅ）在室温和压下对苯的光羰化反应性能,得到了预期的反应产物苯甲醛和苯甲醇。它们均经色－质分析     

某些氨基取代环戊二烯配合物催化1,5-己二烯的高选择性环化

We have interested for some years in studying organic reactions catalyzed by (RCp)2TiCl2/i-C3H7MgX, specially isomerization of non-conjugated dienes[1,2]. Titanocene complexes are also effective for some cyclization reactions[3]. In the case of isomerization of 1,5-hexadiene (HD), such catalysts usually result in a mixture of 1,4-hexadiene, 1,3-hexadiene, 2,4-hexadiene, methylenecyclopentane and methylcyclopentene. Our previous results showed that the product distribution largely depends on the characteristics of the substituents on cyclopentadienyl (Cp) ring[2].     

β-榄香烯的钯、铑催化加氢反应研究

β榄香烯是我国首创的抗癌新药榄香烯乳注射液的主要成分［１］,它的结构是在甲基环己烷骨架上连接有３个烯基取代基（１个乙烯基和２个异丙烯基）．研究β榄香烯３个双键上的化学反应活性,对于榄香烯新反应的开发以及榄香烯类化合物构效关系的研究具有很重要的意义...     

水溶性钌膦配合物催化1-己烯异构化反应的研究

配位催化有催化剂和产物不易分离、溶剂污染环境等问题．而使用水溶性催化体系是克服这些缺点的有效方法之一，并且催化剂还可以循环使用．1984年德国鲁尔化学工业公司用水溶性铑-膦配合物为催化丙烯氢甲酰化生产取得了成功．在众多的水溶性配体中，三-间磺酸钠-三苯基膦[trisodi-     

酰腙钛配合物的合成及其催化乙烯聚合研究

受飞速发展的烯烃聚合工业推动,90年代中后期至今文献报道了大量配合物型烯烃聚合催化剂,其中配位钛、锆配合物展示了较好的应用潜力．如,三齿双胺型钛,β-酮亚胺型锆、8-羟基喹啉-茂型钛和乙酰基萘酚钛等一系列高效烯烃聚合催化剂,而且,Fujita的基于水杨醛亚胺     

烯基取代环戊二烯基钌配合物的合成及晶体结构

本文通过环戊二烯基钠(茂钠)与溴丙烯反应制得单取代的环戊二烯,茂钠与氯丙烯得到双取代的环戊二烯。利用这两个配体合成了烯基取代的环戊二烯基(双三苯膦)氯化钌(1,2)并对化合物(2)进行了晶体结构分析。     

两相催化体系中烯烃氢甲酰化的高区域选择性

采用水溶性铑膦配合物催化剂在两相(水/有机物)体系中进行长链烯烃氢甲酰化反应合成高碳醛,具有反应条件缓和、催化剂与产物容易分离的优点,而且用水作溶剂既便宜、又安全,有利于环境保护,因此引起国内外化学家重视,进行了大量研究[1,2].     

两相催化体系中长链烯烃氢甲酰化反应研究——反应初期的界面化学特征

从界面化学的角度研究了水／有机物两相体系中ＲｈＣｌ（ＣＯ）（ＴＰＰＴＳ）２－ＣＴＡＢ催化１－十二碳烯氢甲酰化反应初期的界面特征。结果表明,催化剂及过量配体的加入,使ＣＴＡＢ的ＣＭＣ降低。样品的光散射及显微照片表明,在ＣＴＡＢ浓度为２．７～６ｍｍｏｌ／ｄｍ＾３范围内,体系中存在着ＣＴＡＢ单体／胶束－Ｏ／Ｗ型乳认间的平衡,在较高ＣＴＡＢ浓度下可能形成Ｏ／Ｗ型微乳;胶束及Ｏ／Ｗ型乳状液滴界面呈负电性,证     

锰配合物催化加氢反应的研究进展

过渡金属催化不饱和有机化合物的加氢反应具有原子经济性高、绿色环保等优点,一直是有机化学研究的重点和难点.当前加氢反应中最常用的催化剂主要是铑、钌、铱、钯等贵金属,以储量丰富的金属锰作为催化剂更符合可持续发展的要求,在过去的几年中,锰催化的醛、酮、酯、腈、酰胺等不饱和化合物的氢化反应得以实现.我们系统地总结了锰配合物在加...     

Crystal Structure of iso-propylcyclopentadienylchloro-(bistriphenylphosphine) ruthenium

１　ＩＮＴＲＯＤＵＣＴＩＯＮＣｙｃｌｏｐｅｎｔａｄｉｅｎｙｌｃｏｍｐｌｅｘｅｓｈａｖｅｂｅｅｎｉｎｔｅｎｓｉｖｅｌｙｓｔｕｄｉｅｄｆｏｒｔｈｅｉｒｒｉｃｈｃｈｅｍｉｃａｌａｎｄｃａｔａｌｙｔｉｃｐｒｏｐｅｒｔｉｅｓ〔１〕．Ｉｔｈａｓｂｅｅｎｗｅｌｌｅｓｔａｂｌｉｓｈｅｄｔｈａｔｔｈｅｒｅｐｌａｃｅｍｅｎｔｏｆａｎη５－ｃｙｃｌｏｐｅｎｔａｄｉｅｎｙｌｌｉｇａｎｄｂｙａｎη５－ｐｅｎｔａｍｅｔｈｙｌｃｙｃｌｏｐｅｎｔａｄｉｅｎｙｌｌｉｇａｎｄｉｎｔｒａｎｓｉｔｉｏｎｍｅｔａｌｃｏｍｐｌｅｘｅｓｒｅ…     

SYNTHESIS OF POLYMER-STABILIZED PLATINUM/RUTHENIUM BIMETALLIC COLLOIDS AND THEIR CATALYTIC PROPERTIES FOR SELECTIVE HYDROGENATION OF CROTONALDEHYDE

Polymer-stabilized platinum/ruthenium bimetallic colloids （Pt/Ru） were synthesized by polyol reduction with microwave irradiation and characterized by TEM and XPS. The colloidal nanoparticles have small and narrow size distributions. Catalytic performance of the Pt/Ru colloidal catalysts was investigated on the selective hydrogenation of crontonaldehyde （CRAL）. A suitable amount of the added metal ions and base can improve the selectivity of CRAL to crotylalcohol （CROL） remarkably. The catalytic activity and the selectivity are dependent on the compositions of bimetallic colloids. Thereinto, PVP-stabilized 9Pt/1Ru colloid with a molar ratio of metals Pt：Ru = 9：1 shows the highest catalytic selectivity 77.3% to CROL at 333 K under 4.0 MPa of hydrogen.     

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。     

3H示踪法研究乙炔均相二聚反应的机理

首次采用氚标记法研究乙炔催化二聚反应机理,结果表明乙炔与Cu(Ⅰ)配位生成中间物同时,伴随乙炔分子上质子向水相转移过程.     

STEREOCHEMISTRY OF (R)-2-METHYLAZIRIDINE COMPLEXES OF COBALT(III) AND DIMERIZATION OF THE LIGAND

Abstract

A cobalt(III) complex containing (R)-2-methylaziridine (R-meaz), [Co(R-meaz)(NH₃)₅]³⁺, was prepared and the two diastereomers arising from the presence of the chiral nitrogen atom (N(R) and N(S)) were separated by column chromatography. Molecular mechanics calculations estimated the N(R)-isomer to be more stable. This result was supported by the x-ray structure determination of the more abundant (ca. 94%) isomer, N(R)-[Co(R-meaz)(NH₃)₅]Br₃H₂O. Crystal data: monoclinic, P2₁, a = 7.357(1), b = 9.780(1), c = 10.426(1) Å, μ = 93.58(1)°, V= 748.7(3) ų, Z= 2. Kinetic studies of isomerization (epimerization) between the two isomers revealed that inversion at the nitrogen center was very slow (5 × 10^?2 M^?1 S^?1at 25 °C). The small rate constant seems to be related to the strained three-membered structure of the meaz ligand. The reaction of Na₃[Co(N0₂)6] and R-meaz yielded a complex containing two dimerized R-meaz chelates, trans-[Co(NO₂)2(di-R-meaz)₂] (di-R-meaz =RR)-α,2-dimethyl-l-aziridineethanamine). The crystal strucrure of trans-[Co(NO₂)₂ (di-R-meaz)₂]C1O₄H₂O was established by x-ray crystallography. Crystal data: orthorhombic, P2₁2₁2₁, a = 11.784(6), b = 21.023(9), c = 8.608(7) Å, V = 2133(2) ų, Z = 4.     

饱和烃C-H键的活化及其配位催化反应

本文评述了饱和烃C—H键活化的最近进展,从配位催化和量子化学的观点,推断了饱和烃C—H键活化及其配位催化反应的机理:首先是它的非定域轨道里的电子对配位在催化剂中心金属的d_z~2/d_■~2-■~2混合轨道上,然后电子从催化剂的HOMO流向底物的LUMO,发生氧化加成反应,生成烷基金属氢化物过渡态,最后经插入反应、还原消除反应,完成整个催化循环。此外,还展望了未来的发展前景。     

EFFECT OF MORPHOLOGICAL STRUCTURE OF AMINOMETHYL POLYSTYRENE RESIN ON THE CATALYTIC PROPERTIES OF POLYMERSUPPORTED RUTHENIUM COMPLEXES

Polymer-supported ruthenium complexes ■-Phen-Ru-①,■-Phen-Ru-②,■-Phen-Ru-③,■-Phen-Ru-④, ■-Phen-Ru-⑤,■-Phen-Ru-⑥and ■-Phen-Ru-⑦were prepared using aminomethyl polystyrenes of different morphological structures as supports.A variety of alcohols were oxidized efficiently into the corresponding ketones, carboxylic acids or aldehydes with iodosylbenzene (PhIO) catalyzed by aminomethyl polystyrene-supported ruthenium complexes under mild reaction conditions in acetonitrile.The influences of morphological struct...     

取代乙酸配体对乙炔二聚反应催化剂性能的影响

研究了取代乙酸配体作为Ｎｉｅｕｌａｎ催化剂对乙炔二聚反应性能的影响。结果表明，不同功能结构数目的影响，结果表明，不同功能结构数目的的氨羧配体均使催化剂的选择性提高。乙炔转化率略有下降，巯基乙酸配体的加入，则改变了乙炔二聚反应的机理，得到以乙醛为主的产物。