正丁基黄原酸根合镉(Ⅱ)的合成和晶体结构

黄原酸配合物以及它们与各种路易斯碱反应的产物得到广泛的研究犤１～４犦。可溶性的黄原酸碱金属盐广泛用于汞、银、镉等金属的萃取分离犤５～７犦，并且这类盐对于汞中毒具有解毒作用犤８犦。E．D．Zelmon等犤９犦对过渡金属黄原酸配合物的非线性光学性质进行了研究。但迄今为止，对黄原酸镉配合物与路易斯碱的反应与结构研究较少。我们首先合成了一种配位聚合物犤Cd（S２CO－n－C４H９）２犦n晶体，然后利用吡啶与犤Cd（S２CO－n－C４H９）２犦n反应破坏其原有配位聚合物的结构，得到了犤Cd（C５H５N）２（S２CO－n－C４H９）…     

立体化学刚性的七配位环戊二烯基三(二苄基二硫代氨基甲酸)钛、锆、铪配合物的合成和性质

二烷基二硫代氨基甲酸基作为良好的双齿配体较易与过渡金属生成高配位的配合物,含有环戊二烯基的高配位钛、锆、铪配合物的研究相继出现^[1-5],这类七配位、18-电子构型的配合物是立体化学刚性,具有独特的光谱性质和结构行为。选择钛、锆和铪二茂二氯化物与三当量的二苄基二硫代氨基甲酸钠反应合成了五种未见报道的七配位配合物,讨论了产物的光谱性质和配位结构。     

Biyclo[2.2.1]heptane as cyclopentane precursor. Part 4 Stereocontrolled syhthesis of a potential intermediate to chromophycane dolastane and clavularane

The regio– and stereoselective synthesis of the keto-esters 20 and 22 are described, the latter being a potential intermediate to several diterpenes. The key steps involve the Diels-Alder cycloaddition between the benzocycloheptenone 5 and cyclopentadiene followed by a regioselective functionalisation of the adduct 6. A remarkable reversal of regioselectivity was observed during oxymercuration of the unsymmetric double bond in 6 and its reduced product 11 leading to 8 and 12 which were subsequently transformed to 20 and 22 respectively.     

相转移催化合成增塑剂BBP和水杨醛的研究

相转移催化合成增塑剂ＢＢＰ和水杨醛的研究郭锡坤，高文华，曾东宇（汕头大学化学系，汕头５１５０６３）关键词相转移催化，季铵盐，聚乙二醇，邻苯二甲酸丁苄酯，水杨醛，增塑剂邻苯二甲酸丁苄酯（增塑剂ＢＢＰ）是一种优良的增塑剂．邻羟基苯甲醛（水杨醛）不仅是重要...     

Environmental pollution study by multielemental neutron activation analysis of garden soil samples from Nagpur City, India

A multielemental instrumental neutron activation analysis (INAA) method has been employed for the determination of 30 elements in seven garden soil samples from Nagpur City and two intercomparison soil standards from IAEA, Vienna and Institute of Radioecology and Applied Nuclear Techniques (IRANT), Slovak Republic. Environmental implications of elemental concentrations in different soils have been discussed.     

Rhodium and palladium β-diketonate determination with on-line supercritical fluid extraction-high performance liquid chromatography via solid phase extraction

 An on-line system of supercritical fluid extraction (SFE) and high performance liquid chromatography (HPLC) via solid phase extraction (SPE) is described for the determination of palladium and rhodium 2,2,6,6-tetramethyl-3,5-heptanedione-(thd) as well as rhodium-acetylacetonate-(acac) and benzylacetonate-(bzac) chelates. The chelates were extracted with supercritical CO₂ from sand and humic acid, concentrated on SPE cartridges and analysed with HPLC. Two cartridge materials were tested and compared to off-line trapping. The percentage of the breakthrough and cartridge retained material were measured in liquid dichloromethane. The SFE conditions could be optimized to separate metal chelates during the extraction. The supercritical fluid (SF) behaviour of different ligands on rhodium were investigated. Received: 19 July 1996/Revised: 11 December 1996/Accepted: 14 December 1996     

Substitution with retention in organoboranes and utilization of the phenomenon for a general synthesis of pure enantiomers

Organoboranes, readily available via the hydroboration of unsaturated organic compounds, exhibit a remarkable versatility in their reactions. The boron atom in these organoboranes can be readily converted into a wide variety of organic groups under very mild conditions, providing simple versatile syntheses of organic compounds. Exploration of these substitution reactions reveal that, with rare exceptions, the organoboranes transfer the alkyl group to other elements of synthetic interest with complete retention of stereochemistry. Recently we have discovered a method of synthesizing essentially optically pure organoborane intermediates. These optically active alkyl groups attached to boron can also be transferred with complete retention of optical activity. Consequently, it is now possible to achieve by a rational synthesis the preparation of almost any optically active compound with a chiral center, either R- or S-, in essentially 100% enantiomeric excess.     

膦取代的羰基铂簇的合成,结构和性质

Pt(PPh_3)_2Cl_2在碱性介质中,与一氧化碳直接进行还原及羰基化反应,得到五种膦取代的羰基铂配合物:Pt_5(μ_2-CO)_5(CO)(PPh_3)_4 1,Pt_3(μ_2-CO)_3(PPh_3)_3 2,Pt_3(μ_2-CO)_3(PPh_3)_4 3,Pt_4(μ_2-CO)_5(PPh_3)_4 4,以及Pt(Cl)(PPh_3)_2(COOCH_3) 5。经X-射线单晶衍射分析,确定了新的三核铂羰基簇2以及配合物5的分子结构。还讨论了1和5的生成机理。     

Dielectric studies of binary mixtures of n -propyl alcohol and ethylenediamine

Dielectric constant (ε’) and dielectric loss (ε") of n-propyl alcohol (PA), ethylenediamine (EDA) and their binary mixtures, for different mole fractions of ethylenediamine have been experimentally measured at 11.15 GHz microwave frequency. Values of density (ρ), viscosity (η) and square refractive index (n _D ² ) of binary mixtures as well as those of pure liquids are reported. Excess square refractive index, viscosity and activation energy of viscous flow have also been estimated. These parameters have been used to explain the formation of complexes in the system.     

不同构象铂(Ⅱ)配合物与G-肌动蛋白作用的光谱研究

The cyclohexamethylene-diamine squaric acid platinum(Ⅱ) complexs(R,R, S,S) binding to G-actin and the consquence conformation change were studied by N-(1-pyrenyl) maleimide(NPM) labeled fluorescence and intrinsic fluorescence. The binding and chemical kinetics were determined by fluorometry. The results showed that when R (Pt/actin molar ratio) was lower than 30, the Pt binded to G-actin strong binding sites(-SH), when R was larger than 30, the Pt binded to G-actin weaker binding sites. The consquence conformation changes were determined by CD. The CD results showed that R was smaller than 60, G-actin α-helix contents decreased slowly, R was larger than 60, G-actin conformation changed obviously. The reaction of R,R complex of platinum(Ⅱ) S,S complex of platinum(Ⅱ) with G-actin was similar to that of with S,S complex of platinum(Ⅱ).