N—取代亚胺二乙酸合铂配合物的合成,表征和反应

1969年,Rosenberg等报道顺式二氯二氨合铂(顺铂)具有抗癌作用,但它有很强的毒副作用和较差的水溶性.1986年,英国正式生产第二代铂抗癌药即碳铂.Khokhar等曾合成一系列N-烷基亚胺二乙酸环己二胺合铂配合物,体外和体内实验均表现出较高的活性和低毒性.其配体以二羧基与铂配位,为八元环结构.显然这不是热力学优势产物.本文合成了一系列二胺铂配合物,结果表明配体以N、O方式与铂配位,具有五元螯合环结构.顺铂与DNA发生交联(主要是与鸟嘌呤N7配位)而抑制癌细胞生长.不同类似物之间的活性差异较大,这可能与它们和DNA作用的动力学有关.我们以鸟苷作模型化合物,用HPLC方法研究了配合物与其作用的动力学,并与顺铂、碳铂进行比较.     

新型N,N'-二(邻氧乙酸)苄叉丙二胺合铜(II)和镍(Ⅱ)及N-(邻氧乙酸)苄叉丙二胺合铜(Ⅱ)的合成、晶体结构及抑菌活性

在乙醇和水的混合溶液中, 将N,N'-二(邻氧乙酸)苄叉丙二胺(1)与氯化铜反应, 获得配合物Cu(Ⅱ)L1·H2O·0.25CH3CH2OH(2)[L1=N,N'-二(邻氧乙酸)苄叉丙二胺]; 当将反应混合溶液的pH值调至8~9, 获得Cu(Ⅱ)ClL2·3H2O(3)[L2=N-(邻氧乙酸)苄叉丙二胺]; 将N,N'-二(邻氧乙酸)苄叉丙二胺(1)与氯化镍反应, 获得配合物Ni(Ⅱ)L1·2.75H2O(4). 用元素分析、1H NMR和IR谱等方法对所合成的化合物1和配合物2~4进行了表征, 并测定了配合物2~4的晶体结构. 在配合物2中, 铜原子为六配位[CuN2O4], 在配合物3中, 铜原子为六配位[CuN2O3Cl], 在配合物4中, 镍原子为六配位[NiN2O4], 三个配合物均为畸变八面体结构. 抑菌活性大小的顺序: 配合物3>配合物2>化合物1.     

新型N,N′-二(邻氧乙酸)苄叉丙二胺合铜(II)和镍(Ⅱ)及N-(邻氧乙酸)苄叉丙二胺合铜(Ⅱ)的合成、晶体结构及抑菌活性

在乙醇和水的混合溶液中,将N,N′-二(邻氧乙酸)苄叉丙二胺(1)与氯化铜反应,获得配合物Cu(Ⅱ)L1.H2O.0.25CH3CH2OH(2)[L1=N,N′-二(邻氧乙酸)苄叉丙二胺];当将反应混合溶液的pH值调至8~9,获得Cu(Ⅱ)ClL2.3H2O(3)[L2=N-(邻氧乙酸)苄叉丙二胺];将N,N′-二(邻氧乙酸)苄叉丙二胺(1)与氯化镍反应,获得配合物Ni(Ⅱ)L1.2.75H2O(4).用元素分析、1H NMR和IR谱等方法对所合成的化合物1和配合物2~4进行了表征,并测定了配合物2~4的晶体结构.在配合物2中,铜原子为六配位[CuN2O4],在配合物3中,铜原子为六配位[CuN2O3Cl],在配合物4中,镍原子为六配位[NiN2O4],三个配合物均为畸变八面体结构.抑菌活性大小的顺序:配合物3>配合物2>化合物1.     

Scchiff碱N-氧化吡啶-2-甲醛缩氨基脲及其铜配合物的合成、晶体结构及谱学性质的研究

合成了Schiff碱N-氧化吡啶-2-甲醛缩氨基脲(PNOS)及其配合物[Cu(PNOS)(NO3)2],并用单晶X射线衍射法测定了配体和配合物结构.PNOS晶体中通过传统氢键形成双层二维网状结构,再由非传统氢键自组装成三维网状结构.配合物[Cu(PNOS)(NO3)2]中的铜为六配位,畸变八面体结构,Schiff碱(PNOS)通过N-氧化吡啶N-O的O原子,亚胺基C=N的N原子,及羰基C=O的O原子与铜配位;一个硝基以单齿配体形式与铜配位,另一个则以双齿配体形式配位.配合物分子通过经典氢键相互作用,形成单层二维网状结构,再通过非经典氢键作用,自组装成双层二维网状结构.     

氢键联结锯齿链形成的新型二维网状铜配合物的合成及晶体结构

氨基酸类化合物如氨基乙酸、亚氨基二乙酸和氨基三乙酸等胺多羧酸有多个配位点 ,可以多种方式和金属离子配位 ,从而得到多种形式的簇合物及一维、二维或三维晶体结构 .我们已经得到了氨基乙酸、亚氨基二乙酸或氨基三乙酸等与稀土和铜的异核配合物 ,并研究了它们的晶体结构[1～ 3] .为深入研究胺多羧酸类配合物的结构特点以及苯环的存在对晶体结构的影响 ,本文合成了一种新型的氨基多羧酸类配合物 N-苯胺叉二乙酸与铜的配合物 ,并测定了其晶体结构 .1　实验部分1 .1　配体 N -苯胺叉二乙酸 [C6H5N ( CH2 COOH) 2 ,H2 L ]的合成　将 5 .…     

Schiff碱N－氧化吡啶－2－甲醛缩氨基脲及其铜配合物的合成、晶体结构及谱学性质的研究

合成了Schiff碱N-氧化吡啶-2-甲醛缩氨基脲（PNOS）及其配合物[Cu(PNOS) (NO_3)_2],并用单晶X射线衍射法测定了配体和配合物结构。PNOS晶体中通过传统 氢键形成双层二维网状结构,再由非传统氢键自组装成三维网状结构。配合物[Cu (PNOS)(NO_3)_2]中的铜为六配位,畸变八面体结构,Schiff碱（PNOS）通过N-氧 化吡啶N-O的O原子,亚胺基C=N的N原子,及羰基C=O的O原子与铜配位;一个硝基以 单齿配体形式与铜配位,另一个则以双齿配体形式配位。配合物分子通过经典氢键 相互作用,形成单层二维网状结构,再通过非经典氢键作用,自组装成双层二维网 状结构。     

基于柔性硫代二乙酸配体的镧系配位聚合物的合成、结构和荧光性质

利用硫代二乙酸配体[thiodiacetic acid = H2tda]与稀土盐[SmCl3·nH2O,DyCl3·nH2O]反应合成了两种新型稀土配合物[Ln2(tda)3(H2O)2]n (Ln = Sm(1), Dy(2)),单晶结构分析表明：两个配合物结构相同,均是通过以共边多面体[Ln2O16]为基本单元的一维稀土金属链拓展而成的二维层状结构。有趣的是,在配合物中,硫代二乙酸配体展现了两种配位模式：双“顺-顺桥式双齿、螫合-桥式三齿”模式和双“螯合-桥式三齿、顺-反桥式双齿”模式;正是通过配体这两种配位方式的连接,上述一维稀土金属链扩展为具有(3,4,5,6)连接(47·68)(44·66) (45·6)(46)(43)拓扑结构的二维网络。荧光性质研究表明,在室温下镝配合物呈现黄色荧光,钐配合物呈现鲑鱼粉色荧光。     

亚硝酰亚铁螯合物——Ⅱ.用Fourier变换红外光谱法研究一氧化氮与亚铁螯合物在水溶液中的配位反应

本文报道了用Fourier变换红外光谱法研究水溶液中一氧化氮与亚铁氨基多膦酸和氨基多羧酸的配位反应。所用的多齿配体有:氨基三甲叉膦酸(NTMP),乙二胺四甲叉膦酸(EDTMP),三乙烯四胺六乙酸(TTHA),二乙烯三胺五乙酸(DTPA),反式-1,2-二胺六环四乙酸(CyDTA),乙二醇二乙醚二胺四乙酸(EGTA)和氨基三乙酸(NTA)。根据~(15)N标记实验,确认了亚硝酰配合物中N—O的特征振动频率。与水合配合物[Fe(H_2O)_5(NO)]~(2+)相比,螯合物中的N—O伸缩振动频率均有“红移”。借助于FTIR技术,考察了亚硝酰配合物与亚硫酸盐或氧气的氧化还原反应。与亚硫酸反应的产物是氨基磺酸一类的化合物。与氧接触后,亚硝酰配合物的N—O特征吸收峰逐渐消失。本文还对不同螯合物体系与NO配位时光谱变化的趋势进行了讨论。     

有机硅聚合物负载硫、硫、氮三齿配体铂配合物的合成与催化性能

 N,N-双(β-甲硫乙基)γ-(三乙氧硅基)丙胺用气相法二氧化硅固载,再与氯亚铂酸钾作用,合成了三齿型铂配合物-聚γ-[N,N-双(β-甲硫乙基)胺基]丙基倍半硅氧烷铂配合物.研究了该配合物对烯烃与三乙氧基硅烷的硅氢加成反应的催化特性.     

吡唑-3,5-二(N-烷基甲酰胺)类配体的双核铜配合物的合成和结构

合成了吡唑-3,5-二(N-烷基甲酰胺)(LH_3)的一系列配合物:(LH_2)_2Cu_2(NO_3)_2·H_2O,L_2Cu_2Na_2·nH_2O。得到了(PEAH_2)_2Cu_2(NO_3)_2·H_2O的单晶结构。(PEAH_3代表吡唑-3,5-二(N-乙基甲酰胺))。从元素分析及红外光谱讨论了不同pH时配合物的配位形式。配合物的ESR谱表明了分子内两个Cu原子间有自旋交换作用。     

Structural study of bismuth complexes with diethylenetriaminepentaacetic acid in aqueous solutions

Bismuth complexes with diethylenetriaminepentaacetic acid were examined in aqueous solutions (pH 4–10) by UV, IR, and NMR spectroscopy. In aqueous solutions, the polydentate ligand is coordinated to bismuth through three N atoms and five O atoms.     

Chiral complexes of Pt with amino acids: synthesis,structure, properties

Short review of syntheses of Pt(II) and Pt(IV) chiral complexes with amino acid ligands and their chemical and spectral studies (IR, electronic absorption, circular dichroism, and NMR spectra) is presented. X-ray diffraction data are reported for key chiral amino acid complexes of Pt and absolute configurations of asymmetric atoms of coordinated ligands are determined. The effect of the absolute configurations of asymmetric carbon, nitrogen, and sulfur atoms of the ligands on optical activity of complexes and on the rates of chemical and biochemical reactions is established.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 83–92.Original Russian Text Copyright © 2005 by Slyudkin, Tulupov.Dedicated to memory of L.M. Volshtein (1904–1983), Professor of Novosibirsk State University D.Sc. (Chem) and O.N. Adrianova (1918–2002), senior associate of Kurnakov Institute of General and Inorganic Chemistry, RAS, who actively participated in most of the studies covered in this review.     

Synthesis, characterization and anti proliferative effect of [Au(en)2]Cl3 and [Au(N-propyl-en)2]Cl3 on human cancer cell lines

Two Au(III) complexes of the type [Au(en)2]Cl3 (2a) and [Au(N-pr-en)2]Cl3 (3a) were synthesized by reacting Auric acid (HAuCl(4)·3H2O) with 2 equiv. ethylenediamine (en) or N-alkyl substituted ethylenediamine ligands. This metallodrug was characterized by various analytical and spectroscopic techniques such as elemental analysis, UV-Vis, Far-IR, 1H NMR and solution 13C as well as solid 13C and 15N NMR. Potentiality of [Au(en)2]Cl3 and [Au(N-pr-en)2]Cl3 as an anti-cancer agent were investigated by measuring some relevant physicochemical and biochemical properties such as stability of Au-N bonds by vibrational stretching from Far IR as well as cytotoxicity and stomach cancer cell inhibiting effect, respectively. The solid-state 15N NMR chemical shift shows that the ligand is strongly bound to gold(III) centre via N atoms. The computational study of 2a shows that the gold coordination sphere adopts distorted square planar geometry with bidentate ethylenediamine ligands acting as a tetradentate chelate. While stable in the solution state, the in vitro biological studies performed with these compounds 2a in solution showed higher activity towards the inhibitory effects of the human cancer cell lines such as prostate cancer (PC-3) and gastric carcinoma (SGC-7901) than that of the N-substituted gold(III) complex (3a). Cytotoxicity of the new compounds has also been estimated in PC-3 and SGC-7901 cells.     

Spectroscopic, kinetic, and mechanistic study of a new mode of coordination of indole derivatives to platinum(II) and palladium(II) ions in complexes

Binding of tryptophan residue to intrinsic metal ions in proteins is unknown, and very little is known about the coordinating abilities of indole. Indole-3-acetamide displaces the solvent ligands from cis-[Pt(en)(sol)2]2+, in which sol is acetone or H2O, in acetone solution and forms the complex cis-[Pt(en)(indole-3-acetamide)]2+ (3) of spiro structure, in which the new bidentate ligand coordinates to the Pt(II) atom via the C(3) atom of the indolyl group and the amide oxygen atom. This structure is supported by 1H, 13C, 15N, and 195Pt NMR spectra and by UV, IR, and mass spectra. Molecular mechanical simulations by Hyperchem and CHARMM methods give consistent structural models; the latter is optimized by density-functional quantum chemical calculations. Dipeptide-like molecules N-(3-indolylacetyl)-L-amino acid in which amino acid is alanine, leucine, isoleucine, valine, aspartic acid, or phenylalanine also displace the solvent ligands in acetone solution and form complexes cis-[Pt(en) N-(3-indolylacetyl)-L-amino acid)]2+ (6), which structurally resemble 3 but exist as two diastereomers, detected by 1H NMR spectroscopy. The bulkier the amino acid moiety, the slower the coordination of these dipeptide-like ligands to the Pt(II) atom. The indolyl group does not coordinate as a unidentate ligand; a second donor atom is necessary for bidentate coordination of this atom and the indolyl C(3) atom. The solvent-displacement reaction is of first and zeroth orders with respect to indole-3-acetamide and cis-[Pt(en)(sol)2]2+, respectively. A mechanism consisting of initial unidentate coordination of the ligand via the amide oxygen atom followed by closing of the spiro ring is supported by 1H NMR data, the kinetic effects of acid and water, and the activation parameters for the displacement reaction. In the case of N-(3-indolylacetyl)-L-phenylalanine, the bulkiest of the entering ligands, the reaction is of first order with respect to both reactants. The bidentate indole-3-acetamide ligand in 3 is readily displaced by (CH3)2SO and 2-methylimidazole, but not by CNO-, CH3COO-, and CH3CN. Complexes cis-[Pd(en)(sol)2]2+ and cis-[Pd(dtco)(sol)2]2+ react with indole-3-acetamide more rapidly than their Pt(II) analogues do and yield complexes similar to 3. This study augments our recent discovery of selective, hydrolytic cleavage of tryptophan-containing peptides by Pd(II) and Pt(II) complexes.     

Different ways of coordination for aminoalkyldiphosphonic acids in palladium(II) complexes

Complexation in the systems K₂PdCl₄-3-amino-1-hydroxypropane-1,1-diyldiphosphonic acid (AHPDP) and K₂PdCl₄-1-aminoethane-1,1-diyldiphosphonic acid (AEDP) was studied using pH-potentiometry, spectrophotometry, and ³¹P NMR spectroscopy. It was found that AHPDP in equimolar complexes is coordinated by Pd(II) in a bidentate fashion through two phosphonate O atoms forming a six-membered chelate [O,O]-ring, while AEDP is coordinated through the N atom and one phosphonate O atom forming a five-membered chelate [N,O]-ring. In 1: 2 complexes of Pd(II) with AEDP, the second AEDP molecule is coordinated by Pd(II) in a similar way to form a second five-membered [N,O]-ring. The latter complexes show cis-trans and syn-anti isomerism. The structural characteristics of the corresponding isomers were calculated at the DFT level of theory and their stabilities were compared.     

Platinum(II) complexes of hydrazides of aspartic and glutamic acids

Mononuclear platinum(II) complexes of the hydrazides of aspartic and glutamic acids have been synthesized and studied. The 1:1 complexes are of the type [Pt(HL)Cl₂]·3H₂O, while the 1:2 complexes are [Pt(HL)₂]Cl₂·3H₂O. In DMF solutions the water molecules are substituted completely by DMF, while in 1:1 (v/v) water-DMF solutions complexes with one DMF and two water molecules are formed. The complexes are characterized using spectroscopic methods (IR, electronic spectra, ESCA), DTA, elemental analysis and titration curves, on the basis of which the ligands are thought to coordinate through the amino- and the hydrazide groups, the carboxylic one remaining deprotonated and non-coordinated.     

8-羟基喹啉存在下水相(两相)中合成取代水杨酸二茂钛配合物

在8-羟基喹啉存在下,分别采用水相法和两相法简便合成了5种取代水杨酸二茂钛配合物,并用元素分析、IR及 1H NMR等手段对配合物进行了结构表征,发现配合物中均不含8-羟基喹啉配体,而是形成以取代水杨酸为双齿配体的六元杂环化合物.用电子吸收光谱分别对两相反应体系(H2O/CHCl3)的水相和有机相进行了动态监测,发现8-羟基喹啉首先通过两相界面与有机相中的二氯二茂钛形成水溶性的过渡性配合物,然后该过渡性配合物再与有机相中的取代水杨酸作用形成了目标配合物.     

Synthesis and dynamic NMR studies of Pt(eta(5)-C(5)Me(5))(CO){C(O)NR(2)} complexes

The formation of Pt(eta(5)-C(5)Me(5))(CO){C(O)NR(2)} (R=Me, Et) complexes was established by spectroscopic analysis. The infrared spectra of these complexes showed a sharp absorption due to the presence of coordinated carbonyl group in the region 2017-2013cm(-1). The N,N-dialkylcarbamoyl ligands showed a characteristic CO stretching absorption in the range 1609-1616cm(-1). The proton NMR spectra of these complexes revealed the expected singlet arising from five equivalent methyl groups on the cyclopentadienyl ring with satellites due to coupling to (195)Pt. The N-methyl and N-ethyl protons exhibited very broad resonances due to restricted rotation about the N-C bond at room temperature. On cooling to -30 degrees C, the N,N-dimethyl protons for complex Pt(eta(5)-C(5)Me(5))(CO){C(O)NMe(2)} showed two sharp singlets at delta 2.86 and 3.09ppm as expected for the static structure. For the N,N-diethyl derivative, Pt(eta(5)-C(5)Me(5))(CO){C(O)NEt(2)}, the methyl protons exhibited only a single triplet at delta 1.06ppm at -10 degrees C due to coupling with the methylene protons. This single resonance arises through accidental overlap as the methylene protons of the ethyl groups are inequivalent at this temperature and each exhibited a quartet at delta 3.33 and 3.70ppm due to coupling with the methyl protons. The singlet resonances for the methyl and ring carbons of the eta(5)-C(5)Me(5) group found in (13)C{(1)H} NMR spectra are illustrative of the chemical equivalence of all the carbon atoms caused by free rotation of the ring in these complexes. The signals attributable to the carbonyl and carbamoyl carbon atom resonances are found downfield as two singlets each with a large coupling constant to platinum. The platinum coupling constants of the downfield resonances could not be identified for Pt(eta(5)-C(5)Me(5))(CO){C(O)NMe(2)} due to presence of impurities.     

Synthesis, characterization, cytotoxic and DNA binding studies of diimine Platinum(II) and Palladium(II) complexes of short hydrocarbon chain ethyldithiocarbamate ligand

Two novel Platinum(II) and Palladium(II) complexes of 2,2′-bipyridine (bpy) with ethyldithiocarbamate (Et-dtc) were synthesized. These complexes were characterized by spectroscopic methods such as ultraviolet-visible, infrared and ¹H NMR as well as conductivity measurements and chemical analysis. In these complexes, the dithiocarbamate ligand coordinates with Pt(II) or Pd(II) center as bidentate with two sulfur atoms. These water soluble complexes were tested for their in vitro anti-tumor activity against chronic myelogenous leukemia cell line, K562. They show Cc₅₀ values lower than those of cisplatin. The mode of binding of the complexes to calf thymus DNA, were investigated by circular dichroism, ultraviolet difference and fluorescence spectroscopy. These complexes can denature DNA at very low concentrations (~100 μM). Both complexes exhibit cooperative binding and presumably intercalate into DNA. Remarkably, most of the experimental results indicate that the tendency of the Pd(II) complex to interact with DNA and its anti-tumor activity against K562 is more than that of its Pt(II) analog.     

Synthesis and characterization of a new platinum(II) complex with L-mimosine

Synthesis and characterization of a new Pt(II)–mimosine complex are described. Elemental, mass spectrometry and thermal analyses for the complex are consistent with the formula [PtCl₂(C₈H₁₀N₂O₄)]·1.5H₂O. ¹³C NMR, ¹⁵N NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and O atoms in a square-planar geometry. The final residue after thermal treatment was identified as metallic Pt. The complex is soluble in dimethylsulfoxide.