THE INTERACTIONS BETWEEN PERIPHERAL AND CENTRAL UNITS IN SUPRAMOLECULAR AND METALLOSUPRAMOLECULAR STRUCTURES: THE CHARACTERIZATION OF SOME MONO-, DI- AND TRINUCLEAR COMPLEXES OF A VICINAL OXIME-IMINE LIGAND

Abstract

The 1:1 molar ratio reaction of p-phenylenediamine with isonitrosoacetylacetone in chloroform led to the formation of the half unit ligand (HL); (1). Two types of the trans octahedral (L)₂Ni 2H₂O complex were characterized; the green molecular complex (2) and the associated supramolecular dark brown complex (3). Molecular association in (3) took place via inter-molecular hydrogen bonding between the amino group of a molecule and the oxygen sites of an adjacent molecule. The 1:1 molar ratio reactions of (2) with the metal acetates M(OAc)₂ (M = divalent nickel, copper or cobalt) produced the self-assembly structure (4) whereby the metal acetate is coordinated to the amino groups of the nickel(II) complex. Reaction of the dinuclear (4) with another metal acetate (1:1 molar ratio) gave the trinuclear terminated structure (5). Similar reactions of (3) with nickel acetate (1:1 or 1:2) led to formation of complexes with metallosupramolecular structures. An antiferromagnetic interaction between the peripheral and central paramagnetic units was observed from those complexes with copper(II) at the peripheral location. In all these cases the metal ions are bridged via the aromatic Schiff-base moiety. The suggested structures of the mono-, di- and trinuclear coordination compounds are in accordance with the analytical, spectral and magnetic moment data.     

钴希夫碱配合物的合成及其氧合机制的研究——Ⅰ.配合物及其氧加合物的合成和表征

本文合成了一系列以水杨醛或萘酚醛同多胺缩合的四齿(N_2O_2)或五齿(N_3O_2)希夫碱为配体的钴希夫碱配合物及它们的氧加合物,用元素分析、红外光谱、磁化率以及ESR谱进行了表征,在续篇中将继续讨论配合物的吸氧行为和氧合机制。     

钴希夫碱配合物的合成及其氧合机制的研究——Ⅰ.配合物及其氧加合物的合成和表征

本文合成了一系列以水杨醛或萘酚醛同多胺缩合的四齿(N₂O₂)或五齿(N₃O₂)希夫碱为配体的钴希夫碱配合物及它们的氧加合物,用元素分析、红外光谱、磁化率以及ESR谱进行了表征,在续篇中将继续讨论配合物的吸氧行为和氧合机制。     

PREPARATION AND CHARACTERIZATION OF COBALT(III) COMPLEXES WITH SARCOSINE AND SOME TETRADENTATE LIGANDS OF THE EDDA TYPE

Abstract

Meridional geometrical isomers of cobalt(III) complexes with sarcosine (N-methylglycine) and tetradentate ligands edda (ethylenediamine-N,N′-diacetate ion), eddp (ethylenediamine-N,N′-di-3-propionate ion) and 1,3-pdda (1,3-propylenediamine-N,N′-diacetate ion) have been prepared. The edda and eddp cobalt(III) complexes were made by the reaction of sarcosine and sodium ethylenediamine-N,N′-diacetato(carbonato)cobaltate(III), and sodium uns-cis-(ethylenediamine-N,N′-di-3-propionato)(carbonato)cobaltate(III) dihydrate, respectively. The previously synthesized pdda-cobalt(III) complex with sarcosine was obtained by a new route by direct synthesis of cobalt(II) chloride hexahydrate with sarcosine and 1,3-pdda in the presents of lead(IV) oxide. Complexes were isolated chromatographically and characterized by elemental analysis, electron absorption spectra, infrared spectra and ¹H NMR spectroscopy.     

SYNTHESES AND MOLECULAR STRUCTURES OF THE ASYMMETRICAL DIPHOSPHINE LIGANDS AND THEIR Pt, Ni ORGANOMETALLIC COMPLEXES

In this paper, we report a novel two-step synthetic method of the symmetrical and asymmetrical diphosphine ligands 1, 2-bis(ditertbutylphosphino)ethane and 1, 2-bis(phenyltertbutylphosphino) ethane, and simultaneously establish a novel synthetic method of diphosphine ligand 1, 4-bis(phosphinocyclopentyl)butane with larger chelate ring. The former was prepared from the reaction of 1, 2-bis(dichlorophosphino)ethane with Grignard reagent andalkyl lithium, respectively, the latter from the reaction of 1, 4-di-Grignard reagent with PCl_3. Furthermore, a series of organometallic complexes of Pt, Ni containing diphosphine chelate ligand were prepared from the reaction of (COD) PtCl_2 complex with diphosphine. These complexes are very stable. Among these complexes, the molecular structures of (d(t-Bu)pe)-PtCl_2, (dPCypb)PtCl_2 and ((n-Bu) (PCyp))_2PtCl_2 complexes have been determined by X-ray diffraction method indicating they are novel complexes. The influence of diphosphine ligand on the molecular structure     

A NEW CYCLOBUTANE SUBSTITUTED SCHIFF BASE LIGAND,SYNTHESIS OF ITS Cd(II), Co(II), Cu(II), Ni(II) AND Zn(II) COMPLEXES AND INVESTIGATION OF THEIR STRUCTURE

Abstract

A new, thiazole derivative ligand, 4-(1-phenyl-1-methylcyclobutane-3-yl)-2-(2-hydroxy-5-bromo benzylidenehydrazino) thiazole (LH), has been synthesized by the reaction of 2-hydroxy-5-bromobenzaldehyde, thiosemicarbazide and subsequently 1-phenyl-1-methyl-3-(2-chloro-1-oxoethyl) cyclobutane. Mononuclear complexes with a metal-ligand ratio of 1 : 2 have been prepared with Cd(II), Co(II), Cu(II), Ni(II) and Zn(II). The authenticity of the ligand and its complexes was established by elemental analyses, IR, ¹³C and ¹H NMR spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC).     

Schiff碱、咪唑金属配合物合成及抗癌活性的荧光筛选研究

本文报道了一类新的Ｓｃｈｉｆｆ碱和咪唑的混合型金属配合物（即水杨醛缩甘氨酸、咪唑金属配合物和２．４—二羟基苯甲醛缩丙氨酸、咪唑金属配合物）的合成，以及用深化乙锭荧光分析法对这类配合物与ＤＮＡ相互作用的研究。结果表明，其中金属镍配合物与ＤＮＡ的作用较明显，可作为具有抗癌作用的药物进行深入研究。     

THE EFFECT OF OXYGEN ON THE INCORPORATION OF MANGANESE,IRON AND COBALT INTO HEMATOPORPHYRIN IX IN GLACIAL ACETIC ACID

Abstract

The results of polarography studies for the reaction of hematoporphyrin IX with Mn(II), Fe(II) and Co(II) ion in acetic acid in the absence and the presence of oxygen are reported. The metal incorporation reaction in the presence of oxygen is quantitative for Mn and Co and incomplete for Fe. In the absence of oxygen, the Mn reaction does not proceed at all, whereas, both the Fe and Co reactions are quantitative.     

CHROMOTROPIC CHANGES OF Cu(II) AND Ni(II) COMPLEXES WITH N2O2 AND N3O2 SCHIFF-BASE LIGANDS IN THE SOLID PHASE

Abstract

Four new Schiff-base ligands have been prepared from the condensation of 3-formyl-4-hy-droxy-1,8-naphthyridin-2-one with different diamines and a triamine, H₂L_a-H₂L_d. Two series of Ni(II) and Cu(II) complexes with the four ligands were also prepared. The ligands and their metal complexes were characterized by chemical analyses, IR, Far-IR, electronic, ESR and mass spectra as well as magnetic measurements and X-ray diffraction patterns.

Different products for Ni(II) and Cu(II) were obtained in similar reactions with the same metal salt, depending on the nature of the ligand. Different geometries were also obtained depending on the counter anion of metal salt. Thus, violet square-planar Cu(II) complexes were obtained with Cu(OAc)₂. H₂O and green octahedral ones with CuCl₂. 2H₂O, except the reaction with ligand H₂L_d which gave only an octahedral product whether the anion was acetate, chloride or perchlorate. Electronic and ESR spectra were used to differentiate between the two geometries of the Cu(II) complexes. The green octahedral Cu(II) complexes undergo irreversible thermochromism to the violet square-planar complexes except the copper complex of the ligand H₂L_d which did not not show any color change and retained its octahedral geometry. Based on the magnetic moments and thermal analyses, only one Ni(II) complex of the Schiffbase ligand H₂L_c undergoes reversible thermochromism from green (octahedral) to red (squareplanar). The reverse change of the thermal product (red) to the parent complex (green) proceeded on exposure to atmospheric air for a few minutes. On the other hand, Ni(II) complexes of ligands H₂L_a and H₂L_b have stable square-planar geometry and all efforts to add other ligands such as H₂O or pyridine to these complexes failed to yield other products. The corresponding Cu(II) complexes were easily transformed to their octahedral geometry by adding H₂O or pyridine and heating.     

分光光度法快速测定钢铁中的锰、磷、硅

用硝酸、过硫酸铵溶解试样,在较高温度下,分别用过硫酸铵光度法测定钢铁中的锰含量,铋磷钼蓝光度法测定磷含量,抗坏血酸硅钼蓝光度法测定硅含量。方法简便、快速、灵敏、准确并已应用于锰、磷、硅自动分析仪。