3-醛基-2-羟基-5-甲基苯甲酸二胺类Schiff碱配体的合成(英文)

合成了3-醛基-2-羟基-5-甲基苯甲酸,将其与乙二胺,1,2-丙二胺,1,3-丙二胺反应合成了3种Sch iff碱配体.用元素分析,IR,MS,1H NMR和13C NMR对它们进行了结构表征.     

Synthesis of alkyl-substituted phosphorus phthalocyanines and triazatetrabenzocorroles

New alkyl-substituted phosphorus phthalocyanines and triazatetrabenzocorroles were synthesized. The structures of these complexes were confirmed by ¹H, ¹³C, and ³¹P NMR spectroscopy, mass spectrometry, and electronic absorption spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1403–1407, July, 2007.     

Chelating Behaviour of Substituted 1-Benzoyl-4-Phenylthiosemicarbazide

The preparation and characterization of a series of new coordination compounds of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) containing o-methyl- or o-chlorobenzoyl-4-phenyl-3-thiosemicarbazide (HMBPT, HCBPT=HL) are reported. The reaction products were investigated by analyses, electrolytic conductance, magnetic susceptibility, reflectance and IR spectral studies. The IR spectra show that HMBPT and HCBPT coordinate with the metal ions via different coordination sites (NS and/or NO). The spectral data support the suggestion that the ligands form his-chelates with Ni(II) and Cu(II) of square planar stereochemistry and of general formulae ML₂·H₂O, where L is the uninegatively charged bidentate ligand. The Co(II) ion forms octahedral and tetrahedral structures with HMBPT and HCBPT, respectively. The ligand field parameters (D₄, B and β) for the Co(II) chelates were calculated using the averaged-ligand-field approximation. The influence of the benzene ring substituents (o-chloro or o-methyl) on the stereochemistry are discussed. Also, the formation of the complexes in solution was tested by the pH-metric method.     

Ligand-protein docking using a quantum stochastic tunneling optimization method

A novel hybrid optimization method called quantum stochastic tunneling has been recently introduced. Here, we report its implementation within a new docking program called EasyDock and a validation with the CCDC/Astex data set of ligand-protein complexes using the PLP score to represent the ligand-protein potential energy surface and ScreenScore to score the ligand-protein binding energies. When taking the top energy-ranked ligand binding mode pose, we were able to predict the correct crystallographic ligand binding mode in up to 75% of the cases. By using this novel optimization method run times for typical docking simulations are significantly shortened.     

四核钴羰基簇合物Co4(CO)8(μ-CO)2(μ4-PSR)2的合成和晶体结构

The title compounds Co4(CO)8(μ-CO)2 (μ4-PSR) [R=-CH3, -C2H5, -C(CH3)3,-(CHa)4CH3] were synthesized by the reaction of Co2(CO)8 with RSPCl2. They were characterized by IR, 1HNMR, elemental analysis. The crystal and molecular structure of Co4(Co)8(μ-CO)2 (μ4-PSC2H5) has been determined by single crystal diffraction method. Crystal data: monoclinic, space group P21 /c, with a=8-445(3), 6=8.562(3), c= 17.125(6)Å, β=104.26 (3)' 9 V=1200.1Å3, Z=2, Dc=1.937gcm-3. Its molecular structure contains an octahedral Co4P2 skeleton which consists of a rectangular four cobalt atoms core and the Co4 core is capped above and below by two quadruply bridging PSR ligands.     

清洁催化氧化环己烯合成己二酸反应中酸性配体的作用

 以30％H2O2为氧源，研究了Na2WO4·2H2O催化氧化环己烯制己二\r\n酸反应中的配体效应．在大多数情况下，配体的酸性越强，目标产物己\r\n二酸的产率越高．尽管一些酚类配体、L（＋）抗坏血酸和8－羟基喹啉\r\n的酸性较弱，但己二酸的产率仍然很高．这表明影响目标产物产率的因\r\n素除配体的酸效应以外，还存在配体的配位效应．邻苯二酚和对苯二酚\r\n等酚类配体的实验结果表明，反应可能是通过络合催化反应机理完成的\r\n．对酸性配体用量及对反应动力学考察结果表明，反应过程中环氧化物\r\n水解为1，2－环己二醇是整个反应的控制步骤，反应体系的酸性起到决\r\n定性的作用．     

d,h-m̈-Alkoxoalkylphosphonato-e-m̈-alkoxo-f-m̈-oxo-bis[trichloroantimon(V)]-Verbindungen

d,h-m?-Alkoxoalkylphosphonato-e-m?-alkoxo-f-m?-oxo-bis[trichloroantimony(V)] Compounds The binuclear antimony(V) complexes Cl₃Sb(O)[R³(R¹O)PO₂](OR²)SbCl₃ 1 to 7 with R¹, R² and R³ = Me or Et in solution slowly exchanges the R² groups between the equatorial oxygen atoms of the Sb₂O₂ ring. The SbO(3)PO(3)Sb ringsystem makes rapid pseudorotation. The resulting isomeres are detected by nmr spectroscopy.     

Synthesis and some properties of phosphorus-substituted azomethines

A series of phosphorus(iii)-substituted azomethines and enamines were synthesized by the reaction of lithium salts of aldimines and ketimines with derivatives of phosphorus(iii) acids. Some properties of the compounds synthesized were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 339–346, February, 1998.     

Copolymerization of butadiene and styrene with a gadolinium tricarboxylate catalyst

Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)₃: R = CH₃, CH₂Cl, CHCl₂, CCl₃, and CF₃], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)₃—(i—Bu)₃Al—Et₂AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)₃: CF₃ > CCl₃ > CHCl₂ > CH₂Cl ～ CH₃. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI₃)₃- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ～ 14.5 mol %) by ¹³C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)₂ and Co(acac)₃-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.     

Melamine cyanurate-microencapsulated red phosphorus flame retardant unreinforced and glass fiber reinforced polyamide 66

A novel microencapsulated red phosphorus (RP) was prepared through the molecular self-assembly of melamine cyanurate (MCA). Compared with the conventional encapsulated RP, MCA-encapsulated RP (MERP) shows simpler and more environment-friendly preparation process higher thermal stability and lower moisture absorption. With MERP filled in unreinforced polyamide 66 (PA66) and glass fiber (GF) reinforced PA66, flame retardant materials with satisfactory flame retardancy and mechanical performance can be obtained. The influence of the MCA/RP ratio on the flame retardancy as well as the condensed phase of MERP flame retardant PA66 was investigated to reveal the nitrogen-phosphorus (N-P) synergistic flame retarding effects between MCA and RP.