2-羟基-3-甲氧基苯甲醛与α-萘胺Schiff碱硝酸稀土配合物的合成与表征

合成邻香兰素(2-羟基-3-甲氧基苯甲醛)与α-萘胺Schiff碱硝酸稀土配合物[LnL~2(NO~3)~2]NO~3(Ln: 镧系元素, L: Schiff碱配体)。配合物由一个中心稀土离子, 两个Schiff碱和三个硝酸根组成, 两个Schiff碱都是氮、氧双配位, 两个硝酸根是双齿配位, 另一硝酸根在配合物外界。中心稀土离子是八配位的, 满足稀土八配位的稳定结构。     

2-羟基-3-甲氧基苯甲醛与α-萘胺Schiff碱硝酸稀土配合物的合成与表征

合成邻香兰素(2-羟基-3-甲氧基苯甲醛)与α-萘胺Schiff碱硝酸稀土配合物[LnL_2(NO_3)_2NO_3(Ln:镧系元素,L:Schiff碱配体)。配合物由一个中心稀土离子,两个Schiff碱和三个硝酸根组成,两个Schiff碱都是氮、氧双配位,两个硝酸根是双齿配位,另一硝酸根在配合物外界。中心稀土离子是八配位的,满足稀土八配位的稳定结构。     

邻香兰素与二胺类双希夫碱镧配合物的合成

某些稀土希夫碱配合物可用于制备核磁共振位移试剂、稀土发光塑料等特殊应用,因而受到人们的重视。估计也会在稀土发光材料方面获得应用。有关邻香兰素(2-羟基-3-甲氧基苯甲醛)与乙二胺(或邻苯二胺、间苯二胺)缩合而成的双希夫碱和镧形成的配合物研究尚未见文献报导。我们在非水体系中用硝酸镧(Ⅲ)和这些双希夫碱反应,合成出固体配合物,研究了它们的组成、结构及某些物理化学性质。     

N,N'-双(2-羟基-3-甲氧基-5-甲基苯甲叉基)乙二胺合钴(Ⅱ) 类似物的合成及其对氧分子的加合性能

2-羟基-3-甲氧基-5-甲基苯甲醛分别与乙二胺,1,2-丙二胺,1,3-丙二胺,2,3-二甲基-2,3-丁二胺及邻苯二胺反应, 合成出一系列二元Schiff 碱型化合物. 测定Schiff碱与钴(Ⅱ)离子配合后的配合物对氧分子的加合常数, 讨论了结构与加合性能之间的关系,配合物中二胺-钴螯合环的刚性对配合物的氧加合性有重要影响     

N,N'-双(2-羟基-3-甲氧基-5-甲基苯甲叉基)乙二胺合钴(Ⅱ) 类似物的合成及其对氧分子的加合性能

2-羟基-3-甲氧基-5-甲基苯甲醛分别与乙二胺,1,2-丙二胺,1,3-丙二胺,2,3-二甲基-2,3-丁二胺及邻苯二胺反应, 合成出一系列二元Schiff 碱型化合物. 测定Schiff碱与钴(Ⅱ)离子配合后的配合物对氧分子的加合常数, 讨论了结构与加合性能之间的关系,配合物中二胺-钴螯合环的刚性对配合物的氧加合性有重要影响     

N,N′-双(2-羟基-3-甲氧基-5-甲基苯甲叉基)乙二胺合钴(Ⅱ)类似物的合成及其对氧分子的加合性能

2-羟基-3-甲氧基-5-甲基苯甲醛分别与乙二胺、1,2-丙二胺、1,3-丙二胺、2,3-二甲基-2,3-丁二胺及邻苯二胺反应,合成出一系列二元Schiff碱型化合物.测定Schiff碱与钴(Ⅱ)离子配合后的配合物对氧分子的加合常数,讨论了结构与加合性能之间的关系.配合物中二胺-钴螯合环的刚性对配合物的氧加合性有重要影响.     

邻香兰素与邻苯二胺双Schiff碱镍配合物的合成, 晶体结构和热分析

合成所得的邻香兰素(2-羟基-3-甲氧基苯甲醛)与邻苯二胺双Schiff碱Ni(II)配合物的晶体[Ni(C~8H~7O~2)2(C~6H~4N~2)].H~2O, 空间群P2~1/n, a=0.8854(2),b=1.9067(5), c=1.1807(4)nm, β=99.43(2)°; Z=4; 结构解析最后的偏正因子R=0.044, R~W=0.052。标题配合物的热分解反应动力学方程式为: dα/dt=A.e^-E/RT.(3/2).(1-α)[-ln(1-α)]^1/3; 热分解反应动力学补偿效应表达式为:lnA=0.1800E+0.0789。     

稀土与邻香兰素二胺类双Schiff碱配合物合成及其性质的研究

在非水体系中首次合成了硝酸稀土(III)的邻香兰素(2-羟基-3-甲氧基苯甲醛)与乙二胺(L^1)、联苯胺(L^2)、邻苯二胺(L^3)和间苯二胺(L^4)的双Schiff碱配合物(1-8)。通过测定红外光谱、摩尔电导、X射线衍射和X射线光电子能谱推断了配合物的结构和键合情况,配合物的中心金属离子与配体中的二个氮原子、二个氧原子和二个硝酸根中的四个氧原子配位,其配位数为8。通过热重及差热分析发现配合物在低于230℃时很稳定,对于同一配体与不同中心金属离子形成的配合物来说,其热稳定性随稀土离子半径的减小而降低。在77K时测试了铕配合物的激发光谱和荧光光谱,观察到Eu^3^+的特征发射峰。     

邻香兰素缩对甲苯胺Schiff碱稀土配合物的合成、晶体结构和热分解动力学机制

合成了2-甲氧基-6-[(4-甲基苯基)亚胺甲基]-苯酚Schiff碱(C15H15NO2,简写为HL)的3个稀土配合物[Pr(NO3)3(HL)2](1),[Nd(NO3)3(HL)2](2),[Er(NO3)3(HL)2]·0.5H2O(3),结构通过单晶X射线衍射分析确定,并用元素分析、摩尔电导、IR、1HNMR和紫外可见光谱进行表征。化合物1~3中,Schiff碱作为二齿配体与中心离子发生配位,稀土离子均采用十配位的双帽四方反棱柱构型,分别与两个Schiff碱中的4个氧原子、3个硝酸根中的6个氧原子发生配位。通过TG-DTG研究了配合物的热分解过程,用非等温动力学方法研究了配合物3的热分解动力学机制。     

邻香草醛缩组氨酸Schiff碱及其镧配合物的合成与生物活性

合成了2个新的化合物——邻香草醛缩组氨酸Schiff碱及其镧配合物.通过元素分析、X射线衍射、红外光谱、紫外-可见光谱、热重-差热分析及化学分析等对它们进行了表征.结果表明,邻香草醛缩组氨酸Schiff碱为2-[(2-羟基-3-甲氧基-苯亚甲基)-氨基]-3-(2-咪唑基)-丙酸一水合物(C14H15N3O4·H2O),Schiff碱镧配合物为二氯-{2-[(2-羟基-3-甲氧基-苯亚甲基)-氨基]-3-(2-咪唑基)-丙酸}合镧(Ⅲ)三水合物[La(C14H15N3O4)Cl2·3H2O].应用生物微量热法研究了这2个化合物的生物活性,在301.15 K下测定了2个化合物存在时粟酒裂殖酵母细胞代谢的产热曲线,计算得到了粟酒裂殖酵母细胞生长速率常数(k)、传代时间(tG)、总热效应(Qtotal)、抑制率(I)及半抑制浓度(IC50)等热动力学参数.结果表明,随着C14H15N3O4·H2O和La(C14H15N3O4)Cl2·3H2O浓度的增加,k和Qtotal减小,tG和I增加,IC50分别为0.2585和0.2488mmol/L.     

Heterodinuclear Ln[bond]Na complexes with an asymmetrical macrocyclic compartmental Schiff base

Heterodinuclear lanthanide(III)-sodium(I) complexes [LnNa(L)(Cl)(2)(CH(3)OH)] (Ln=La[bond]Nd, Sm[bond]Lu), where H(2)L is a [1+1] asymmetric compartmental macrocyclic ligand containing a N(3)O(2) Schiff base and a O(3)O(2) crown-ether-like coordination site, have been prepared and characterized by IR, (1)H, (13)C, and (23)Na NMR spectroscopy, mass spectrometry, and electron microscopy. In the solid state, the lanthanide(III) ions coordinate the Schiff-base N(3)O(2) site, and the sodium ion occupies the O(3)O(2) crownlike cavity, as shown by the X-ray crystal structures of the Nd, Eu, Gd, and Yb derivatives. In these complexes, the lanthanide(III) ion is coordinated by two chlorine atoms in the trans position and by three nitrogen and two negatively charged phenol oxygen atoms of the Schiff base, and the ion is heptacoordinated with a pentagonal bipyramidal geometry. The sodium ion is coordinated by three etheric oxygen atoms and the two phenolic oxygens that act as a bridge. A methanol molecule is also coordinated in the apical position of the resulting pentagonal pyramidal polyhedron. A detailed (1)H and (13)C NMR study was carried out in CD(3)OD for both diamagnetic and paramagnetic heterodinuclear complexes [LnNa(L)(Cl)(2)(CH(3)OH)]. The complexes are also isostructural in solution, and their structures parallel those found in the solid state. Moreover, some significative distances determined in the solid state and in solution are comparable. Finally, the potential use of these complexes as molecular probes for the selective recognition of specific metal ions has been tested. In particular, their ability to act as shift reagents and the selectivity of the O(3)O(2) site towards Li(+), Ca(2+), and K(+) were investigated by (23)Na NMR spectroscopy.     

Syntheses, Structures and Coordination Behavior of Central Hydroxyl Group Containing Polydentate Ligands

Proteins containing dinuclear Cu (II), Zn (II) centers play paramount roles in biology1. As mimetic of metal-dependent esterase, dinuclear Cu (II) and Zn (II) complexes have received a great deal of attentions2~6. They are of interest in the field of biomimetic chemistry to provide an improved understanding of the function of the biological sites and as potential catalysts for substrate oxidations. Schiff base type polydentate ligands which contain centeral hydroxyl group have been wid…     

双水杨醛1,10-癸二胺Schiff碱稀土配合物的合成和表征

合成了双水杨醛缩1,10-癸二胺Sch iff碱配体(C24H32N2O2,以L表示)与稀土Ln3+的15种新的固体配合物[LnL(NO3)3].nH2O(Ln=La,Ce,Pr,Nd,Sm,Eu,n=0;Ln=Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y,n=1).利用元素分析、摩尔电导、红外光谱、热分析等方法进行表征.中心金属离子Ln3+与Sch iff碱配体中的酚羟基氧以及硝酸根中的氧发生配位,配位数为8.     

The Preparation, Characterization and Biological Activity of Palladium(II) and Platinum(II) Complexes of Tridentate NNS Ligands Derived from S-methyl- and S-benzyldithiocarbazates and the X-ray Crystal Structure of the [Pd(mpasme)Cl] Complex

New complexes of general formula, [M(NNS)Cl] (M = Pd^II, Pt^II; NNS = anionic forms of the 6-methyl-2-formylpyridine Schiff bases of S-methyl- and S-benzyldithiocarbazates) have been prepared and characterized by a variety of physico-chemical techniques. Based on conductance and spectral evidence, a square-planar structure is assigned to these complexes. The crystal and molecular structure of the [Pd(mpasme)Cl] complex (mpasme=anionic form of the 6-methyl-2-formylpyridine Schiff base of S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted square-planar geometry with the ligand coordinated to the palladium(II) ion via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the fourth coordination position around the palladium(II) ion is occupied by the chloride ligand. The distortion from a regular square-planar geometry is ascribed to the restricted bite angle of the ligand. Both the Schiff bases exhibit strong cytotoxicity against the human ovarian cancer (Caov-3) cell lines, the S-methyl derivative being two times more active than the S-benzyl derivative. The [Pt(mpasme)Cl] complex is moderately active but the palladium(II) complex is weakly active against this cancer. None of the complexes of Hmpsbz are active against Caov-3. The Schiff base, Hmpasme exhibits moderate activity against the bacteria, MRSA, P. aeruginosa and S. typhimurium but is inactive against B. subtilis. Coordination of the ligand with palladium(II) substantially reduces its activity. The Schiff base, Hmpasbz and its palladium(II) and platinum(II) complexes are inactive against these bacteria. The Schiff bases and their palladium(II) and platinum (II) complexes are inactive against the pathogenic fungi, C. albican, Aspergillus ochraceous and Saccharomyces cerevisiae.     

Complexes of zinc,cadmium and mercury(II) with the zwitter-ionic form of NN′-ethylenebis (salicylideneimine)

The Schiff base NN′-ethylenebis(salicylideneimine), H₂ salen reacts with hydrous and anhydrous Zinc, Cadmium and Mercury(II) salts to give complexes M(H₂ salen)X₂·nH₂O (M = Zn, Cd, Hg; XCl, Br, I, NO₃; MZn, X₂SO₄; n = 0?2). Spectroscopic and other evidence indicated that; (i) halide and sulphate are coordinated to the metal ion, whereas the nitrate group is ionic in mercury nitrate compound and covalently bonded in zinc and cadmium nitrato complexes, (ii) the Schiff base is coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms, which carry the protons transferred from phenolic groups on coordination, (iii) therefore the coordination numbers suggested are 4-, in mercury and 4- or 6- in zinc and cadmium Schiff base complexes.     

稀土席夫碱邻菲咯啉三元配合物的合成及其生物活性研究

以稀土氯化物、席夫碱水杨醛缩苯丙氨酸和邻菲咯啉为配体,在无水乙醇溶液中反应,制备了一类新型稀土三元配合物,通过元素分析、摩尔电导、核磁共振、红外光谱、拉曼光谱,确定了该配合物的化学组成:RE(L)( Phen) Cl (H2O)(RE= Ce3 ,Sm3 , Eu3 ,Y3 ,Gd 3 ;L=席夫碱水杨醛缩苯丙氨酸;Phen=邻菲咯啉).通过抗菌实验对其抑菌效果进行研究,结果表明配合物对大肠杆菌、金黄色葡萄球菌及白色念珠菌都有较强的抑制作用,抗菌谱广;用流式细胞检测法对配合物使癌细胞凋亡能力做了初步研究,证明其具有使癌细胞凋亡的效果.     

Synthesis and characterization of copper(II) and nickel(II) complexes of the Schiff base derived from 2-(2-aminophenyl)benzimidazole and salicylaldehyde

Summary Copper(II) and nickel(II) complexes with the Schiff base derived from 2-(2-aminophenyl)benzimidazole and salicylaldehyde, L, have been prepared. They are of the general types ML₂X₂ (M = Ni or Cu and X = Cl, Br, NO₃ or ClO₄) and NiL(NCS)₂.The compounds have been characterized by elemental analyses, magnetic measurements, e.s.r., electronic and i.r. spectra studies. The i.r. spectra suggest that the molecule, and not the anion, of the Schiff base is coordinated as a bidentate ligand with the metal ion. Possible structures for the complexes have been proposed.     

Synthesis and vibrational spectroscopy of halotrichite and bilinite

The new uranyl complexes with tetradentate unsymmetrical N₂O₂ Schiff base ligands were synthesized and characterized by IR, UV–vis, NMR and elemental analysis. The DMF solvent is coordinated to uranyl complexes. The thermogravimetry (TG) and differential thermoanalysis (DTA) of the uranyl complexes were carried out in the range of 20–700 °C. The UO₂L¹ complex was decomposed in two and the others were decomposed in three stages. Up to 100 °C, the coordinated solvent was released then the Schiff base ligands were decomposed in one or two steps. Decomposition of synthesized complexes is related to the Schiff base characteristics. The thermal decomposition reaction is first order for the studied complexes.     

金刚烷胺邻香兰素Schiff碱稀土配合物的合成、表征及抗菌活性研究

The new solid complexes [LnL₂(NO₃)₂]NO₃ (L=C₁₈H₂₃NO₂, N-2-hydroxy-3-methoxy-benzaldehyde-1-aminoadamanantane, Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) of rare earth nitrates with Schiff base derived from o-vanillin and adamantaneamine have been synthesized in non-aqueous system and characterized by elemental analysis, molar conductance, infrared spectra, ¹H NMR spectra, thermal analysis. The coordination modes of the bonding in these complexes were discussed and the possible structure were proposed. Every central Ln(Ⅲ) ion in the complexes coordinates with both two Schiff base ligands via four oxygen atoms of the phenol hydroxy groups and methoxy groups and two nitrates via their four oxygen atoms. Their coordination numbers are eight. In addition, the antibacterial activity of the Schiff base ligand and the complexes were studied.