COMPLEXES OF GALLIUM(III) WITH HYDROXYAROMATIC LIGANDS

Abstract

The equilibria between gallium(III) ion and selected hydroxyaromatic and dihydroxyaromatic ligands at 25°C, μ=0.100 M (KNO₃) have been determined. Potentiometric measurements on 1:1, 2:1, and 3:1 molar ratios of ligand to Ga(III) have been made as a function of degree of neutralization over the entire accessible ?log [H⁺] scale. Calculations were carried out so as to take account of competing hydrolytic reactions, and formation constants of gallium(III) with chromotropic acid, 8-hydroxyquinoline-5-sulfonic acid, 5-sulfosalicylic acid, and 1,2-dihydroxy-benzene-3,5-disulfonic acid were obtained. Stable hydroxo chelates do not form under the reaction conditions employed. The protonation constants of the ligands and the formation constants of the gallium chelates are discussed and compared with previously published work on these gallium chelates and on chelates of “analogous” metal ions such as those of Fe(III) and A1(III).     

有机镓配合物的合成及其质谱

本文通过三环戊基镓与取代苯酚, 有机酸, 氨基酸反应合成了八个新的有机镓配合物, 这些配合物经过元素分析、质谱、核磁共振或红外光谱鉴定; 质谱研究表明这些配合物均以二聚体的形式存在。     

N503萃取镓及其机理的研究

镓的提取过去多采用中和、置换等老力法,其流程长,收率又低。近年来,溶剂萃取法显示出极大的优越性,因此,在镓的萃取分离方面国内外也给予了极大的重视,并已有综述^[1-3]。目前,从盐酸体系中萃取镓常用的工业萃取剂有:甲基异丁基酮(MIBK)^[4-7]、磷酸三丁酯(TBP)^[8-12]、三辛胺(TOA)^[13-17]等。但由于MIBK水溶性大、易挥发、TBP对聚氯乙烯萃取设备有严重的溶胀性、TOA的萃取选择性较     

金属镓促进的巴豆基溴与醛的反应

α－甲基烯丙基醇是合成一些大环内酯（ｍａｃｒｏｌｉｄｅ），聚醚抗生素（ｐｏｌｙｅｔｈｅｒａｎｔｉｂｉｏｔｉｃｓ）和信息素的重要中间体［１］。立体选择性地合成α－甲基烯丙基醇是当今最富挑战性的课题之一。正是因为这类化合物具有广泛的合成价值，以致于有三十...     

含有稠环侧链的聚硅氧烷的合成及其对加成型高温硫化硅橡胶性能的影响

将含有多乙烯基的聚硅氧烷与菲式环戊二烯酮和苊式环戊二烯酮分别在α-氯萘中进行Diels-Alder反应,生成含有稠环侧链的聚硅氧烷.该聚硅氧烷具有较好的耐热性.将其作为组分制成高温加成型硅橡胶,综合性能达到较高水平(高模量).随着其用量的增加,可使其耐热性能得到较大改善。     

INORGANIC RINGS AND CLUSTERS AS SINGLE-SOURCE PRECURSORS TOWARD STOICHIOMETRY CONTROLLED SYNTHESIS OF MATERIALS: GAS PHASE CHEMISTRY IN COMMAND

Potential of the inorganic rings and clusters as single-source precursors to 13–15 binary materials and composites is examined employing quantum-chemical methods. Importance of the gas phase association reactions during MOCVD processes from organometallic and hydride precursors is emphasized. Generation of the gas phase [HMYH]_n clusters (M = Al,Ga,In; Y = N,P,As) with large oligomerization degree (n ≥ 30) is thermodynamically favorable even at high temperature conditions (1000 K) for all M,Y pairs. High stability of the N-containing clusters makes mixed metal oligomer imidometallanes excellent single-source precursors for the stoichiometry-controlled MOCVD of 13–15 composites.     

FORMATION OF THIADIAZOLE AND THIAZOLE RINGS FROM HETEROCYCLES WITH A THIOAMIDE SIDE CHAIN

Abstract

Substituted or unsubstituted thioureido heterocycles can be successfully used for the formation of a new thiadiazole or thiazole ring. For example, a fused thiadiazolo ring is formed either from carbethoxythioureido- or carbethoxymethylthioureido-heterocycles (I). The reaction proceeds by oxidative cyclization and can be performed in the presence of various oxidizing agents. On the other hand, some reducing agents convert II back into I. A particular case represents the reaction between 2-chloro-3-aminopyridine and carbethoxy isothiocyanate giving directly III (R = = COOEt), although the reaction must proceed via an intermediate like I (n = O).     

镓及其氧化物中杂质元素分析方法研究进展

作者从原子发射光谱法、原子吸收光谱法、吸光光度法、电化学分析法、活化分析法、质谱分析法六个方面,综述镓及其氧化物中杂质元素分析方法的进展（引用文献３２篇）。     

石墨炉原子吸收光谱法测定高温合金中镓

研究了普通石墨管、平台石墨管和涂钼普通石墨管对镓的测定性能.得出涂钼普通石墨管对镓的测定灵敏度和重现性均好于其他石墨管.从而建立了一种更为满意的石墨炉原子吸收测定高温合金中镓的新方法.     

A New Class of Ruthenium Carbene Complexes: Synthesis and Structures of Highly Efficient Catalysts for Olefin Metathesis

Cationic Ru^II carbene complexes with tBu₂PCH₂PtBu₂ (dtbpm) as a chelating ligand, which are accessible by chloride abstraction from neutral precursors [(κ²-dtbpm)Cl₂Ru=CHR] with trimethylsilyl triflate, are established as highly efficient ring opening metathesis polymerization catalysts (see scheme). Solv=solvent.     

苯甲酰丙酮缩乙二胺与镧系元素多核配合物的合成及表征

本文合成了8个镧系元素与苯甲酰丙酮缩乙二胺希夫碱配合物。经元素分析、摩尔电导、热分析、电子光谱、红外光谱与¹H NMR等表征,确证为双核配合物:Ln₂(L)₃(NO₃)₆·2H₂O(Ln=La、Ce、Pr、Nd、Sm、Gd、Dy及Er;L=苯甲酰丙酮缩乙二胺)。文中探讨了配体空间位阻等影响,并提出了所合成配合物的可能结构。     

Fluorescence Switches Triggered by Metal Ions

Molecular switches 1 with a modular architecture whose functional principle is based on conformational changes around two acetylene axes were developed. By systematic screening of various metal ions, it was found that especially Pb²⁺ ions effectively trigger the switching event. The reporting of this event takes place by the change of the ratio between excimer and monomer fluorescence emission of two pyrene moieties.     

三甲基镓与氮杂冠醚配合物的合成与表征(Ⅰ)

合成了八个新型的三甲基镓与侧链含酚羟基的氮杂冠醚所生成的配合物,用元素分析、红外、核磁共振和质谱的方法进行了表征,推断了它们的结构。配合物结构的研究对于探讨ＭＯ新源的ＭＯＣＶＤ技术研究具有重要意义     

丙酮酸·邻菲咯啉·稀土三元固体配合物的合成和表征

丙酮酸在生物体内具有生理功能,它与稀土的二元配合物巳有报导。近期的研究结果表明某些稀土的邻菲咯啉三元配合物有一定的抑菌能力。本文报道丙酮酸(pyr-H)、邻菲咯啉(phen)稀土三元固体配合物的合成与表征结果。 按硝酸稀土:邻菲咯啉:丙酮酸(摩尔比)=1:1:3,将一定量的硝酸稀土加入无水乙醇中,溶解完全后,加入计算量丙酮酸,加热搅拌半小时,然后慢慢加入含计算量邻菲咯啉的     

稀土组氨酸配合物的合成和性质研究

本文合成了十二个稀土与Ｌ－组氨酸（Ｌ－Ｈｉｓ）的固体配合物，元素分析结果表明配合物的组成为Ｌｎ（Ｈｉｓ）３（ＮＯ３）３２Ｈ２Ｏ（Ｌｎ＝Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｅｒ，Ｔｍ）。并通过配合物的ＩＲ、ＵＶ、Ｈ－ＮＭＲ、ＴＧ－ＤＴＡ、磁化率及在水中的摩尔电导等的研究，表征了这些配合物的物理化学性质，结果表明稀土组氨配合物中配体通过羟基氧原子与镧系离子配位。     

REACTIONS OF THE RHODIUM TRIFLUOROACETATE DIMER WITH NUCLEOSIDES AND NUCLEOTIDES

Abstract

Complexes of rhodium trifluoroacetate with adenosine (ado), adenosine-5′-momophosphate (AMP), cytidine (cyd), guanosine (guo) and inosine (ino) have been prepared from aqueous or methanolic solutions. They were characterized by elemental analysis, magnetic susceptibility measurements, mass spectra, infrared, visible and nuclear magnetic resonance spectroscopies. In some cases their formation was followed by NMR prior to isolation. They all proved to be diamagnetic and in every compound contain two ligand molecules per rhodium dimer except for the ado complex where the ratio is 1:1. In the solid state it was found that adenosine interacts with the metal via the N(1) and N(7) atoms, its nucleotide through N(7), whereas in the case of cyd, guo and ino their exocyclic oxygen atoms take part in coordination. Solution study seem highly interesting since in some cases more than one species appear.     

三甲基镓与氮杂冠醚配合物的合成与表征（Ⅰ)

合成了八个新型的三甲基镓与侧链含酚羟基的氮杂冠醚所生成的配合物,用元素分析、红外、核磁共振和质谱的方法进行了表征,推断了它们的结构。配合物结构的研究对于探讨MO新源的MOCVD技术研究具有重要意义。