铑配合物催化甲醇羰基化反应的性能和机理

本文合成了２－丁酸甲酯吡啶与四羰基二氯二铑形成的螯合形配合物，并用Ｘ射线光电子能谱（ＸＰＳ），红外光谱（ＩＲ）及核磁共振（ＮＭＲ）研究确定了其配位结构特征，通过甲醇羰基化制备乙酸的反应揭示了其结构特征对催化剂活性及稳定性的影响，并提出了可能的反应机理。     

Exchange reactions of copper complexes with amines

Square planar mixed ligand complexes of the type [CuLL′] where L = 5-chlorosalicylaldehyde and L′ = acetoacetanilide, have been synthesized on treatment with ammonia. Amine exchange of the above Schiff base complexes has been carried out on treatment with different amines. The reaction with ethanol amine is quite interesting compared to other amines. It reacts with 5-chlorosalicylaldehyde to form a Schiff base, while the β-diketone part is removed in the complex formation. All the complexes were characterized by elemental analysis, spectral studies, magnetic measurement, TLC, and conductane.     

Syntheses, Structures and Coordination Behavior of Central Hydroxyl Group Containing Polydentate Ligands

Proteins containing dinuclear Cu (II), Zn (II) centers play paramount roles in biology1. As mimetic of metal-dependent esterase, dinuclear Cu (II) and Zn (II) complexes have received a great deal of attentions2~6. They are of interest in the field of biomimetic chemistry to provide an improved understanding of the function of the biological sites and as potential catalysts for substrate oxidations. Schiff base type polydentate ligands which contain centeral hydroxyl group have been wid…     

Synthesis of o-carborane-C-carboxylates of certain natural terpene alcohols, sterols, phenols, and camphar oxime

Previously unreported esters 1b–20b were synthesized from natural terpene alcohols, sterols, plant phenols, and camphar oxime (1a–20a) by reaction with o-carborane-C-carboxylic acid chloride. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 434–436, September–October, 2006.     

Recovery of pyridine from aqueous solution by membrane pervaporation

Three different membranes, based on poly(dimethylsiloxane) (PDMS), cation-exchange material and poly(vinyl alcohol) (PVA) respectively, were tudied for the separation of pyridine-water mixtures by pervaporation. The PDMS membrane was preferentially permeable to pyridine and the other two were selective towards water. Three membranes showed different permeation performance, allowing the application of the technique to the separation of feeds of different composition. The temperature profile of the permeability suggests that it is possible to carry out the operation at an elevated temperature in order to achieve high productivity. A combination of the three types of membranes was designed for the production of anhydrous pyridine from dilute pyridine aqueous solution by pervaporation.     

二茂铁甲酰丙酮缩氨基硫脲金属配合物研究

将二茂铁甲酰丙酮与硫代氨基脲在水 -乙醇介质中进行缩合反应 ,得金属有机多齿配体C5H5Fe C5H4COCH2 C(CH3 ) =NNHCSNH2 (简记作 Fc TS) ,该配体分别与 d-过渡金属 [Cu( )、Co( )、Ni( )、Mn( ) ]、 B族金属 [Zn( )、Cd( ) ]及主族金属 [Pb( ) ]乙酸盐反应 ,合成了分子式为 (Fc TS) 2 M(CH3 COO) 2 的 7个新型配合物。经元素分析、IR、UV- Vis,1 H HMR、摩尔电导及固体电导的测定对配合物组成、结构、波谱性质和导电性能进行了研究。     

Syntheses and Characterizations of Novel One-dimensional Coordination Polymers Self-assembled from Co(NCS)_2 and Flexible Diester-bridged Pyridine-based Ligands

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New methods for data analysis of isothermal titration calorimetry

Heat divided by ligand concentration vs. heat, similar to the Scatchard plot, was introduced to obtain the equilibrium constant (K) and the enthalpy of binding (DH) using isothermal titration calorimetry data. Values of K and DH obtained by this linear pseudo-Scatchard plot for a system with a set of independent binding sites (such as binding fluoride ions on urease and monosaccharide methyl a-D-mannopyranoside on concavalin A) were remarkably like that obtained from a normal fitting Wiseman method and other our technical methods. On applying this graphical method to study the binding of copper ion on myelin basic protein (MBP), a concave downward curve obtained was consistent with the positive cooperativity in the binding. A graphical fitting by simple method for determination of thermodynamic parameters was also introduced. This method is general, without any assumption and restriction made in previous method. This general method was applied to the product inhibition study of adenosine deaminase. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chiral ditopic receptors. Application to palladium-catalyzed allylic alkylation

Chiral pyridinooxazoline, quinolinooxazoline, bis(oxazolino)pyridine (pybox), and bisoxazoline (box) derivatives containing crown ether residues were prepared. Some of the ligands were assessed in substrate binding studies and in palladium catalyzed allylic alkylations.     

手性氨基酚配体及其衍生物在不对称催化中的应用

综述了手性氨基酚配体及其衍生物的研究进展, 着重介绍其在不对称催化烷基化、烯基化、Michael加成、aldol反应及环丙化等反应中的应用.