铜(Ⅰ，Ⅱ)配合物的合成、结构与性质

在室温、有关配体存在下,利用金属铜粉和过氧化苯甲酰的氧化加成配位反应合成了四种铜(Ⅱ)配合物(配体分别为联吡啶、双二苯基膦乙烷、2-氨基吡啶、苯并咪唑)。同时又利用双齿有机膦配体(dppm=双二苯基膦甲烷,dppe=双二苯基膦乙烷,dppp=双二苯基膦丙烷,dppb=双二苯基膦丁烷)和金属铜盐的还原取代反应合成了四种一价铜(Ⅱ)配合物。通过元素分析确定了配合物的组成,经X射线四圆单晶衍射确定了配合物的分子结构,配合物的晶体结构由直接法和Fourier合成方法解出。利用电子光谱等手段研究了氧化加成配位和还原取代配位反应的机理。初步建立了一套简单有效的合成铜(Ⅰ,Ⅱ)配合物的新方法。     

多功能基膦酰胺Pd（Ⅱ）配合物促进烯烃加氢催化性能的研究

研究了一系列二苯基膦乙酰胺腙的Pd(Ⅱ）配合物新催化剂在常压条件下催化烯烃加氢的性能。发现P、N二齿配位结构的催化剂显出好的催化活性,配体苯环上的供电子基对催化有明显的促进作用;P、N、O三齿配位模式的催化剂无催化作用。     

含混合配体双核铜（I）配合物的合成及荧光光谱

合成了含双二苯基膦甲烷（dppm)和邻菲咯啉（phen)混合配体的双核铜（I）配合物[Cu(dppm)(phen)]2(NO3)21,并经X射线单晶结构分析表征了配合物的结构，研究了配合物的荧光光谱特征，配合物1的结构分析表明，dppm作为桥式双齿配体、phen作为双齿配体分别与铜原子形成四面体配位结构，硝酸根离子位于配合物外界。     

含硫希夫碱配合物的研究Ⅱ

合成了由硫代对称二氨基脲和α－乙酰吡啶及邻氯苯甲醛缩合的两种新的含硫希夫碱配体，及它们与Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）的配合物，所有化合物用元素分析、红外光谱、紫外一可见光谱、磁化率、摩尔电导等测试进行了表征．对某些配合物还进行了生物活性的初步试验。     

铂（Ⅱ）－二－双－（二苯基膦）乙烷离子配合物的晶体结构及Pt（Ⅱ）－CN￣－键断裂

铂（Ⅱ）－二－双－（二苯基膦）乙烷离子配合物的晶体结构及Ｐｔ（Ⅱ）－ＣＮ￣－键断裂杨帆，吕士杰，傅宏祥（结构化学国家重点实验室，中国科学院福建物质结构研究所，福州３５０００２）（羰基合成与选择氧化国家重点实验室，中国科学院兰州化学物理研究所，７３００...     

双核铜（Ⅱ）配体合成研究进展

本文综述了最近三十年在双核铜（Ⅱ）配体合成方面的进展。     

二苯甲酮双缩硫代对称二氨基脲Sn（Ⅱ）、Rb（Ⅱ）配合物的电化学合成

芳香醛、酮缩氨基硫脲及其金属配合物因其具有良好的抑菌、抗癌和抗病毒的生物活性^[1-3]而受到人们的重视,以往芳香醛、酮缩氨基硫脲金属配合物的合成,大都是配体和相应金属的盐在乙醇溶液中完成,用金属阳极在含配体的非水溶剂中的电化学氧化直接合成金属配合物报道较少^[4],而非水溶剂电化学阳极溶出法是合成低价金属化合物的有效途径之一^[5]。为此,我们合成了新希夫碱二苯甲酮双缩硫代对称二氨基脲（HL）,并用金属阳极电化学氧化法合成了该配体的Sn(Ⅱ）、Rb（Ⅱ）的配合物。通过元素分析、IRF、UV等手段对配体、配合物进行了结构测定和表征。     

双（二苯基膦）丁烷的双核银配合物晶体结构

报导了双（二苯基膦）丁烷的双核银配合物－［Ａｇ（Ｐｈ_２ＰＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２ＰＰｈ_２）－（ＮＯ_３）］_２的合成及晶体结构分析。晶体属于单斜晶系，空间群为Ｐ２_１／ｎ，晶胞参数为：ａ＝１２．８２１（３），ｂ＝１１．２４４（９），ｃ＝１９．３８６（９），β＝１０５．９４（３）°，Ｖ＝２６８７．２~３，Ｚ＝２，Ｄ_ｃ＝１．４７４ｇ／ｃｍ~３，Ｍ_ｒ＝１１９２．７，Ｆ（０００）＝１２１６，μ＝８．８７３ｃｍ~（－１）。晶体结构由直接法和Ｆｏｕｒｉｅｒ合成解出，使用对角块矩阵和全矩阵最小二乘法对原子参数进行修正，最后偏离因子Ｒ＝０．０５６，Ｒ_ｗ＝０．０６８，其中２６３４个Ｉ＞３σ（Ⅰ）的可观察点参加了结构修正，单晶结构分析结果表明，在该配合物中，配体双（二苯基膦）丁烷（ｄｐｐｂ）中的磷原子直接与银离子配位，硝酸根也以双齿配位形式存在，中心银离子的配位采用畸变的四面体构型，整个分子是一个二聚物。     

非对称取代卟啉钴（Ⅱ）轴向配位反应的热力学研究

合成了非对称对位取代卟啉钴（Ⅱ）（５－（４－乙酰胺基苯基）－１０，１５，２０－三（４－甲基苯基）卟啉钴（Ⅱ））用分光光度法测量了该体系与一系列含咪唑基配体（２－甲基咪唑（２－ＭｅＩｍ），Ｎ－甲基咪唑（Ｎ－ＭｅＩｍ）２－乙基－４－甲基咪唑（ＥＭＩｍ）克霉唑（ＧＭＺ）轴向配位反应的平衡常数，研究结果表明，配体的尺寸及取代基的位置将向轴向配合物的稳定性产物影响，其平衡常数呈现ＫＧＭＺ〉ＫＮ－ＭｅＩｍ〉Ｋ     

镍（Ⅱ）、钴（Ⅱ）、锌（Ⅱ）－N－（间位取代苯基）亚氨基二乙酸体系的量热研究

使用改进的ＲＤ—１型热导式自动量热计测定了Ｎｉ（Ⅱ）、Ｃｏ（Ⅱ）、Ｚｎ（Ⅱ）－Ｎ－（间位取代苯基）亚氨基二乙酸三个二元体系的表观生成热．当将其与它们的配体的质子化热相关联时，发现在两者之间存在着良好的直线焓关系．这些金属离子配合物的生成热也符合Ｉｒｖｉｎｇ—Ｗｉｌｌｉａｍｓ序列，即有Ｃｏ（Ⅱ）＜Ｎｉ（Ⅱ）＞Ｚｎ（Ⅱ）的顺序．配体上取代基不同，其生成热的大小有Ｃｌ－＞ＣＨ３Ｏ－＞Ｈ－＞ＣＨ３－的顺序．从两级生成热来比较，有一级大于二级的普遍规律．本文详细地讨论了这些规律．     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

线性反馈抑制螺旋波

A class of excitable media described by the Fitzhugh-Nagumo equation is investigated. Based on the stable and self adaptive theory, the error between the systems grid variables and the standard sampling of the periodical signal or constant signal was feed back into the system both globally and locally. When the controller was then shut off, automatically, the whole system became homogeneous. Additionally, the scheme was tested under noisy conditions. The numerical simulations results demonstrate its effectiveness. The system reached a homogeneous state and a spiral wave was converted into a target wave, resulting in a wonderful pattern emerging using a different controller. The scheme proved robust in resisting the effects of noise.     

Synthesis and characterization of inorganic solid electrolytes of Li2O-SiO2-P2O5 and Li2O-TiO2-SiO2-P2O5 systems

The lithium-ion-conducting inorganic solid electrolytes in the oxide systems Li₂O-SiO₂-P₂O₅ and Li₂O-TiO₂-SiO₂-P₂O₅ were prepared by the solid-state reaction, and the electrolyte pellet made by cold-pressing method had diameter of 13 mm and was about 1 mm thick. Phase identification and surface morphology of the products were carried out by X-ray diffraction and scanning electron microscopy. Ionic conductivity of the pellets was investigated through ac impedance. The results show that the adding of other cations can improve the ionic conductivity of the solid electrolyte, and the sintering temperature and duration can influence the ionic conductivity. The maximum ionic conductivity in the samples is 9.9 × 10⁻⁴ S/cm in the Li₂O-TiO₂-SiO₂-P₂O₅ system. Original Russian Text ? W. Li, M. Wang, Z.H. Li, X.F. Shang, H. Wang, Y.W. Wang, Y.B. Xu, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 11, pp. 1341–1345.     

酞菁染料的金属化和溴化与光物理影响的研究

以α位(2,4-二特戊基)苯氧基邻苯二腈作为环合前体,制备了多种金属酞菁,产物经元素分析、紫外、红外、核磁氢谱等分析手段进行表征.并选择了部分酞菁进行溴化,其中着重研究了不同中心金属以及溴化对染料Q带吸收的影响.结果表明,酞菁染料的金属化对于其Q带吸收影响很大,多数染料金属化后会出现蓝移,而选择合适的条件进行溴化,可以使得金属酞菁的Q带吸收出现一定程度的红移,其中部分溴化金属酞菁的吸收波长与光信息产业中使用的近红外激光器很接近,具有潜在的实用价值.     

PREPARATION OF MONODISPERSE CROSSLINKED POLYMER MICROSPHERES HAVING CHLOROMETHYL GROUP BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene) (poly(CMSt-co-DVB)) microspheres were prepared by distillation-precipitation copolymerization of chloromethylstyrene (CMSt) and divinylbenzene (DVB) in neat acetonitrile. The polymer particles had clean surfaces due to the absence of any added stabilizer. The size of the particles ranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014. The effects of monomer feed in copolymerization on the microsphere formation were described. The polymer microspheres were characterized by SEM and chlorinity elemental analysis.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Change of water structure by solvents and polymers

Viscosity measurements have been made of water-solvent and water-polymer solutions in a temperature range of 20–60 centigrades. A medium structure temperatureT ₀ was calculated from the Vogel-equation. Water has a structure temperature of 140–150 K, its decrease indicates structure breakage, an increase structure promotion. Pyridine, dioxane, dimethylformamide and urea are structure breakers. This is explained by a shift of the equilibrium — bonded water molecules — nonbonded — to the right. Acetone shows hydrophobic bonding in the same concentration range of 0–10 mole % as the normal alcohols. They are quasifree liquids-structure temperature zero-in the pure state. This is explained by hydrogen bridged dimer formation with the exception of tert-butanol. Its 3 methylgroups sterically prevent dimer formation and cause structuring. Adding urea to methanol-water solutions breaks water structure according to urea concentration but extends the hydrophobic bonding maximum over the whole diagram. Glucose-water solutions have a minimum in the structure temperature diagram. Its left side indicates waterstructure breakage, its right side formation of a new structure forced upon water by the sugar. The equilibrium can be formulated: Waterlike bonded-nonbonded-hetero (solvent)-like bonded, Ribose also shows this minimum but after a short range of heterobondedness the structure is completely broken to nonbondedness.The polymers dextrane and polyvinylpyrrolidone are strong waterstructure breakers. Dextrane much stronger than PVP, it breaks to nonbondedness while PVP maintains a certain structuring, perhaps indicating heterobonding at higher concentrations. Polyacrylamide is a strong structurebreaker. It resembles urea in this sense. Perhaps the solvationwater structure of the NH₂ groups is very different from pure waterstructure. Polyacrylicacid breaks waterstructure completely, if sodiumchloride is added waterstructure is rebuilt again. The only waterstructure promoting polymer is natural gelatine. Perhaps this structure is different from pure water or the watermolecule equilibrium is shifted towards bondedness. The structure temperatures of pure polyethyleneglycoles show a minimum with increasing molecular weight. The high structure temperature of the small chains is explained by long chain assoziates formation through hydrogen bridging. This liquid of long assoziate chains is structured and has a high structure temperature. With increasing molecular weight ringformation instead of linear assoziation becomes possible. These neutral rings form a free liquid. Long chains again have a linear structure and the structure temperature increases at higher molecular weights. Existence of linear chain assoziation of low molecular PEGs is proved with their breakage by adding the chain terminating methanol.Dedicated to Prof. Dr. F. H. Müller.Herrn Chemotechniker D. Ziegler möchte ich für die sorgfältige Durchführung der Messungen sehr danken.Dem Verband der Chemischen Industrie danke ich sehr für die Ermöglichung der Arbeit.     

Time,gravity and the exterior angle of parallelism

Applying calculus to the horizontal and vertical unit hyperbolas we derive the obtuse exterior and the acute angle of parallelism formulas for the arc length of a unit circle. When the analogous arc length of a hyperbola is figured, we further define metric distance with radian measure. Employing a non-conventional velocity of light formula, we explain several aspects of physics with a logical geometry. The hyperbolic geometry Lobacevskii angle of parallelism is mathematically measured to agree with the physical measure, without using the gravitational constant, but rather the electromagnetic spectrum and geodesics. Space is hereby measured with units of radians and time. Half-angle formulas for slopes and boosts pertain to spinor algebra. The new light velocity is justified when its derivative results in Einstein's mass–energy formula. Relativity is reformulated with these half-angle formulas.