Spectrochemical Properties of Noncubical Transition Metal Complexes in Solutions. XIV. Angular Overlap Studies of bis(Salicylidene-2-aminothiazole)Copper(II) in Various Solvents

The copper(II) complex [Cu(sat)], where Hsat is salicylidene-2-aminothiazole (bidentate Schiff - base), was studied in variety of solvents. In the solid state, the complex is black. It has been characterized by elemental analysis, solubility in common solvents, molar conductivity, and ultraviolet (UV) and visible (Vis) spectroscopy. The complex is easily soluble in common solvents such as chloroform, dimethylformamide, dimethyl sulfoxide, and 1,4-dioxane. The known crystal structure of similar compounds shows planar coordination geometry for the copper center. Combined multitechnique experiments have been applied to confirm the structure of the complex in solutions. The molar conductivities indicate their nonelectrolyte properties in all these solvents. The spectroscopic measurements were used to study the coordination properties of donoratoms and their bonding abilities.     

新型含葡萄糖基手性Salen配体及其Mn3+、Fe3+、Co2+、Cu3+配合物的合成与表征

A novel chiral Salen ligand with a glucose moiety was synthesized from the condensation of 1,2:5,6-di-O-isopropylidene-3-O-methylene-[5-(3-tert-butyl-2-hydroxy benzaldehyde)]-α-D-glucofuranose with (1R,2R)-1,2-diaminocyclohexane. Several chiral complexes of Mn³⁺, Fe³⁺, Co²⁺ and Cu²⁺ were prepared from this ligand. Both the ligand and the complexes were characterized by elemental analysis, NMR, IR, MS, and UV-Vis.     

工业原料铁制备浆态床FT合成用的Fe-Cu-K-Si催化剂的探索

费托合成技术是公认的将煤基合成气转化为液体燃料和化工原料的重要技术途径。虽然固定床费托合成技术从五十年代起已经工业运转，但是浆态床费托合成技术由于其传热性能好，可直接使用第二代气化炉生产的富CO合成气，反应器结构简单，单台反应器生产能力大，开工率高，产品结构合理，     

THERMODYNAMIC STUDY ON ADSORPTION OF AROMATIC SULFONIC ACIDS ONTO MACROPOROUS WEAK BASE ANION EXCHANGER FROM AQUEOUS SOLUTIONS

 The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, p-toluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K-313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy,and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.     

新型1,1′-双乙酰基二茂铁席夫碱的合成

通过1,1′-双乙酰基二茂铁双肼腙与芳醛(酮)的缩合反应,合成了6个新型1,1′-双乙酰基二茂铁席夫碱,其结构经1H NMR,IR和元素分析表征。     

新型芳基双西佛碱及其Ni（Ⅱ）,Fe（Ⅲ）配合物的合成

新型芳基双西佛碱及其Ｎｉ（Ⅱ），Ｆｅ（Ⅲ）配合物的合成蓝仲薇，严洪兴，李莉，余孝其（四川大学化学系，成都６１００６４）关键词西佛碱，合成，催化活性西佛碱除广泛用作螯合剂、稳定剂、分析试剂和生物活性剂以外。近年研究表明，其单核和双核金属配合物对于催化作...     

潜手性Schiff碱不对称催化还原反应研究进展

对近年来潜手性Schiff碱的不对称催化氢化的发展状况按照均相、非均相及氢转移催化氢化三种类型进行了较为详尽的综述.     

双冠醚研究(Ⅳ)——Schiff碱型和仲胺型双-(苯并15冠-5)对碱金属苦味酸盐的萃取行为

仲胺型双冠醚与四苯硼酸碱金属盐在丙酮溶液中。25℃下的电导说明它们与Na~+可能形成1∶1络合物(冠醚单元∶金属离子),而与K~+、Rb~+、Cs~+离子则形成2∶1络合物。用Schlff碱型和仲胺型双-(苯并15-冠-5)在水-氯仿体系中进行萃取,测量了分配比D和萃取平衡常数K,发现后者的K值均大于前者。双冠醚F_2对K~+的萃取能力最强,选择性最佳。     

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Our recent extensive research on Lewis acid catalysts with a weak base for the cationic polymerization of vinyl ethers led to unprecedented living reaction systems: fast living polymerization within 1–3 s; a wide choice of metal halides containing Al, Sn, Fe, Ti, Zr, Hf, Zn, Ga, In, Si, Ge, and Bi; and heterogeneously catalyzed living polymerization with Fe₂O₃. The use of added bases for the stabilization of the propagating carbocation and the appropriate selection of Lewis acid catalysts were crucial to the success of such new types of living polymerizations. In addition, the base‐stabilized living polymerization allowed the quantitative synthesis of star‐shaped polymers with a narrow molecular weight distribution via polymer‐linking reactions and the precision synthesis and self‐assembly of stimuli‐responsive block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1801–1813, 2007.     

Kinetics and Mechanism of the Cerium(IV) Oxidation of Arnold's Base and the Protonation and Hydroxylation of Michler's Hydrol Blue

In aqueous H₂SO₄, Ce(IV) ion oxidizes rapidly Arnold's base((p-Me₂NC₆H₄)₂CH₂, Ar₂CH₂) to the protonated species of Michler's hydrol((p-Me₂NC₆H₄)₂CHOH, Ar₂CHOH) and Michler's hydrol blue((p-Me₂NC₆H₄)₂CH⁺, Ar₂CH⁺). With Ar₂CH₂ in excess, the rate law of the Ce(IV)-Ar₂CH₂ reaction in 0.100 M H₂SO₄ is expressed -d[Ce(IV)]/dt = k_app[Ar₂CH₂]₀[Ce(IV)] with k_app = 199 ± 8M^?1s^?1 at25°C. When the consumption of Ce(IV) ion is nearly complete, the characteristic blue color of Ar₂CH⁺ ion starts to appear; later it fades relatively slowly. The electron transfer of this reaction takes place on the nitrogen atom rather than on the methylene carbon atom. The dissociation of the binuclear complex [Ce(III)ArCHAr-Ce(III)] is responsible for the appearance of the Ar₂CH⁺ dye whereas the protonation reaction causes the dye to fade. In highly acidic solution, the rate law of the protonation reaction of Michler's hydrol blue is -d[Ar₂CH⁺]/dt = k_obs[Ar₂CH⁺] where K_obs = ((ac + 1)[H*] + bc[H⁺]²)/(a + b[H⁺]) (in HClO₄) and k_obs= ((ac + 1 + e[HSO₄^?])[H⁺] + bc[H⁺]² + d[HSO₄^?] + q[HSO₄^?]²/[H⁺])/(a + b[H⁺] + f[HSO₄^?] + g[HSO₄^?]/[H⁺]) (in H₂SO₄), and at 25°C and μ = 0.1 M, a = 0.0870 M s, b = 0.655 s, c = 0.202 M^?1s^?1, d = 0.110, e = 0.0070 M^?1, f = 0.156 s, g = 0.156 s, and q = 0.124. In highly basic solution, the rate law of the hydroxylation reaction of Michler's hydrol blue is -d[Ar₂CH⁺]/dt = k_OH[OH^?]₀[Ar₂CH⁺] with k_OH = 174 ± 1 M^?1s^?1 at 25°C and μ = 0.1 M. The protonation reaction of Michler's hydrol blue takes place predominantly via hydrolysis whereas its hydroxylation occurs predominantly via the path of direct OH attack.