钇与亚胺基二乙酸配合物的合成及晶体结构

合成了钇与亚胺基二乙酸的配合物，用Ｘ射线衍射法测定了配合物的单晶结构，化学式为［Ｙ２｛Ｈ２Ｎ（ＣＨ２ＣＯＯ）２｝（Ｈ２Ｏ）４］（ＣｌＯ４）２·１．２５Ｈ２Ｏ。晶体属三斜晶系，Ｐ１↑－空间群。晶胞参数：ａ＝０．９２５４（１）ｎｍ，ｂ＝０．９９２２（１）ｎｍ，ｃ＝１．０６５８（２）ｎｍ，α＝７１．４８１（１０）°，β＝７７．９５０（１０）°，γ＝６５．３５０（１０）°，Ｖ＝０．８４０１（２）＾３，Ｚ＝     

亲水性亚胺二乙酸基螯合树脂合成与性能的研究

本文通过聚丙烯酸甲酯树脂与过量的乙二胺反应,形成含有伯胺基的聚丙烯酰胺树脂,然后再与氯乙酸反应,形成含有亚胺二乙酸基团的树脂(凝胶型和大孔型)。研究了聚丙烯酸甲酯树脂与乙二胺反应条件。本文所合成的螯合树脂比以聚苯乙烯为骨架的亚胺二乙酸树脂具有较高的金属吸着容量和较快的交换速度,树脂在酸碱中稳定性良好。     

双马来腈二亚胺合铂与DNA的作用

本文以紫外-可见光谱、荧光光谱及黏度法研究了双马来腈二亚胺合铂与DNA的作用。紫外-可见光谱的研究表明,与DNA作用后,双马来腈二亚胺合铂在可见区的吸收显示出了减色效应,并伴随着吸收峰的蓝移。Scatchard图的分析结果表明,双马来腈二亚胺合铂与DNA的作用位点与溴化乙锭不同。黏度法实验表明,双马来腈二亚胺合铂与DNA作用后降低了DNA的相对黏度。这些研究结果表明,双马来腈二亚胺合铂以静电作用方式与DNA结合。本研究有助于深入理解双马来腈二亚胺合铂的作用机理并开发这种潜在的新型光动力治疗剂。     

四氯合铂（Ⅳ）类配合物的合成表征及其抗癌作用

顺铂作为第一代无机抗癌药物已被广泛使用,但副作用较大。碳铂是第二代无机抗癌药物,虽肾毒性和肠胃道反应比顺铂低,但在某些肿瘤治疗方面,活性低于顺铂。最近,Aderson等发现tetraplatin(tetrachloro(d,1-trans)1,2-dimino cyclohexane platinum     

二胸苷二氨合铂的合成及其平衡常数的测定

用逐步中和法,在pH=9.0的条件下合成了二胸苷二氨合铂,用Sephadex G-10分离得到纯配合物,并用元素分析、TG、DTA和~(13)CNMR对此进行了表征。用~1H NMR法测定和计算了配位反应的平衡常数,其值为1gK_1=9.95,1gK_2=6.92。     

多齿铂配合物的合成和NMR研究

本文制备了一些新的铂配合物cis-PtA_2X_2,式中A为NH_3,i-prNH_2;X_2H_2为天冬酸,硫代二乙酸和N-烷基亚胺二乙酸,并用~1H,~(13)CNMR和IR技术研究了不同条件下配体与铂的配位方式。数据表明,硫代二乙酸以S,O,O方式;天冬酸以N,O方式与铂配位,而N-烷基亚胺二乙酸可以N,O(pH>5.5)或N,O,O(pH<4)两种不同方式与铂配位。同时考察了某些配合物在水中的稳定性。     

β—二酮型钴和镍配合物液晶的合成与表征

合成了β-二酮型钴和镍配合物。通过元素分析、IR、NMR、热台偏光显微镜、DSC和WAXS等观测,表明两个配合物皆为热致性向列型液晶。     

N,N′-二乙酸取代含噻吩环氮杂冠醚配体及其稀土配合物的合成与表征

A new N,N′-diacetic acid substituted azacrown ether containing thiophere ring ligand(H₂L) has been synthesized by using salicylaldehyde, diamine, thiophene and bromoacetic acid as starting materials. With this ligand, its lanthanide complexes [ML(NO₃)]·nH₂O(M=La,Ce,Pr,Nd,Sm,Eu,Dy,Er,Yb;n=2 or 3) are prepared. These compounds are characterized by elemental analysis, IR, ¹H NMR, MS and conductivity measurements. The results show that ether oxygen, carboxy oxygen, nitrogen atoms and nitrate ion are coordinated to the metal ion.     

N,N''''-二乙酸取代含噻吩环氮杂冠醚配体及其稀土配合物的合成与表征

N－功能化大环不仅环的空腔大小及环上配位原子种类对不同离子具有配位选择性，其功能化的官能团也会对大环配体的性质和选择性有很大影响，这类大环及其金属配合物，在药物试剂犤１犦，金属离子的分离与回收犤２犦，环境保护和新材料犤３犦等方面都有着广泛的应用前景。人们对N－功能化氮氧杂大环及其配合物研究较多犤４～６犦，而对N－功能化的氮氧硫杂大环研究并不多。为了进一步研究和开发这类大环配体及其性质，我们合成了一个新的功能化的大环配体（４，５：１４，１５二苯并－３，１６－二氧－２１－硫－７，１２－二氮双环犤１６…     

Cyclic Bis-alkylidene Complexes of Titanium and Zirconium: Synthesis,Characterization, and Reaction

Transition-metal alkylidenes have exhibited wide applications in organometallic chemistry and synthetic organic chemistry, however, cyclic Schrock-carbene-like bis-alkylidenes of group 4 metals with a four-electron donor from an alkylidene have not been reported. Herein, the synthesis and characterization of five-membered cyclic bis-alkylidenes of titanium ( 4 a , b ) and zirconium ( 5 a , b ) are reported, as the first well-defined group 4 metallacyclopentatrienes, by two-electron reduction of their corresponding titana- and zirconacyclopentadienes. DFT analyses of 4 a show a four-electron donor (σ-donation and π-donation) from an alkylidene carbon to the metal center. The reaction of 4 a with N,N′-diisopropylcarbodiimide (DIC) leads to the [2+2]-cycloaddition product 6 . Compound 4 a reacted with CO, affording the oxycyclopentadienyl titanium complex 7 . These reactivities demonstrate the multiple metal–carbon bond character. The reactions of 4 a or 5 a with cyclooctatetraene (COT) or azobenzene afforded sandwich titanium complex 8 or diphenylhydrazine-coordinated zirconacyclopentadiene 9 , respectively, which exhibit two-electron reductive ability.     

Synthesis,Characterization, and Crystal Structures of Diruthenium Complexes Containing Bridging Salicylato Ligands

The thermal reaction of Ru₃(CO)₁₂ ( 1 ) with salicylic acid, in the presence of triphenylphosphine, pyridine, or dimethylsulfoxide, afforded the dinuclear complexes Ru₂(CO)₄(μ‐O₂CC₆H₄OH)₂L₂ ( 2 ) [L = PPh₃ ( 2a ). C₅H₅N ( 2b ); (CH₃)₂SO ( 2c )]. Complex 2b was further reacted with the aromatic dimmines 2,2′‐dipyridine or 1,10‐phenanthroline to give the cationic diruthenium complexes [Ru₂(CO)₂(μ‐CO)₂(μ‐O₂CC₆H₄OH)(N∩N)₂]⁺ ( 3 ) [(N∩N) = 2,2′‐dipyridine ( 3a ); 1,10‐phenanthroline ( 3b )], which were isolated as their tetraphenylborate salts. All five novel complexes were characterized spectroscopically and analytically. For 2a – 2b and 3a – 3b , single‐crystal X‐ray diffraction studies were also carried out.     

两种溴代苯甲酸-铽配合物的合成、晶体结构与性质表征

溶液法合成了2种配合物[Tb(2-BrBA)₂(CH₃COO)(2，2′-bipy)]₂ (1)和[Tb(3-BrBA)₃(2，2′-bipy)]₂·2(3-HBrBA)·2H₂O (2)(2-BrBA=2-bromobenzoate，3-BrBA=3-bromobenzoate，2，2′-bipy=2，2′-bipyridine)，并用X-射线单晶衍射方法测定了其晶体结构。配合物1和2均属于三斜晶系和P1空间群。四元混配配合物1是具有反演中心的二聚体，其中Tb³⁺离子同时与2种不同的羧酸配体配位。4个2-BrBA以双齿桥联的方式把2个Tb³⁺离子联结起来，而乙酸根和2，2′-bipy分子则分别以双齿螯合的方式与Tb³⁺离子配位。配合物2是三元混配配合物，2个Tb³⁺离子通过4个双齿桥联的3-BrBA联结而成具有反演中心的二聚体，每个Tb³⁺离子还同时与1个双齿螯合的3-BrBA和1个2，2′-bipy分子配位。配合物1和2在紫外灯照射下能发出强烈的绿光，而且在它们的荧光光谱中都存在4条谱线：489、545、585和621 nm，分别对应于Tb³⁺离子的 ⁵D₄ → ⁷F₆、 ⁵D₄ → ⁷F₅、 ⁵D₄→ ⁷F₄和 ⁵D₄→ ⁷F₃跃迁。     

二茂铁丙烯酸稀土配合物的合成与表征

本文用氯化稀土(RECl_3)与二茂铁丙烯酸钠盐(LNa)在无水乙醇中反应,合成了13种新的稀土配合物。由元素分析、红外光谱和热谱分析确定配合物的组成为:(C_5H_5FeC_5H_4CH=CHCOO)_3RE·H_O(RE=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb),配体羧基以双齿对称螯合方式与稀土离子配位。经X射线粉末衍射分析,对其晶体结构进行了初步探讨。     

含茂基、N-苯基苯甲异羟肟酸镧系有机配合物的合成与表征

合成了以茂基－N－苯基苯甲异羟肟酸为配体的一系列新型稀土金属有机配合物Cp2LnL(Cp＝η^5－C5H5；Ln=Sm，Nd，Gd，Dy，Ho，Er，Yb Pr；L＝C6H5CONOC6H5）。产物经元素分析、IR和MS表征。     

两个外消旋双U形稀土单核配合物的合成、晶体结构及其表征

对氨基苯磺酸(p-AbsH),邻菲咯啉(phen)与稀土硝酸盐在pH=6～7的水溶液中反应,合成了2个新颖的双U形单核配合物[Ln(O-p-Abs)₂(phen)₂(H₂O)₃](NO₃)·2H₂O,其中Ln=La(1)和Ce(2)。X-射线单晶结构测定表明,2种晶体属异质同晶,正交晶系,Pccn空间群。在2个配合物中,Ln(Ⅲ)离子与5个O原子和4个N原子配位,形成1个畸变的三冠三棱柱体LnN₄O₅配位多面体,其中2个氧原子来自于2个对氨基苯磺酸根的磺酸基,另3个O原子则由配位水分子提供,4个N原子来自2个Phen。p-Abs与phen通过π-π作用构成具有手性的螺旋双U形结构,每个晶胞中含有2对构型相反的[Ln(O-p-Abs)₂(phen)₂(H₂O)₃]⁺,整个晶体呈外消旋,2种异构体分子间通过phen间的π-π作用构成超分子螺旋链,并通过氢键作用形成三维超分子结构。     

Synthesis and Characterization of New CIS-1,4-Diaminocyclohexane and Piperidine Platinum(II) Complexes Containing Disubstituted Sulfide Groups

Abstract

A series of cationic platinum(II) complexes of the type [Pt(cis-1,4-DACH)(R′R″S)Cl]NO₃ and [Pt(PIP)₂(R′R″S)Cl]NO₃ (where cis-1,4-DACH = cis-1,4-diaminocyclohexane; PIP = piperidine; and R′R″S = dimethylsulfide, diethylsulfide, dipropylsulfide, diisopropylsulfide, dibutylsulfide, diphenylsulfide, dibenzylsulfide, methylphenylsulfide, or methyl-p-tolylsulfide) have been synthesized and characterized by elemental analysis and infrared, ¹H, and ¹⁹⁵Pt nuclear magnetic resonance spectroscopy.     

Synthesis and Characterization of a Series of Water Soluble Amidomalonato-(lR,2R-Cyclohexanediamine)Platinum(II) Complexes

Abstract

A new series of water soluble platinum(II) complexes of the type [Pt(DACH)[R-CH(COO)₂]], wherein DACH represents IR,2R-cyclohexanediamine and R represents formamido. acetamido, (penta-O-acctyl-gluconyl)amino, and gluconylamino have been synthesized. The modes of binding of amidodicarboxylic acid derivatives in these complexes have been determined by various spectroscopic techniques: ¹H, ¹³ C, and ¹⁹⁵PtNMR; 2D-COSY{¹H-¹H} and 2D-HETCOSY{¹H-¹³C} NMR, MS(FAB), IR and conductivity measurements.     

Synthesis,Thermal Isomerization in Solution and in Solid Phase of the Complexes [Pt(RCN)2Cl2]

The interaction of the clathrate Pt₆Cl₁₂ · 0.1 EtCl · 5.7H₂O with RCN nitriles results in cis-[Pt(PhCH₂CN)₂Cl₂] and in [Pt(RCN)₂Cl₂] (R = CH₂CO₂Et, Ph) complexes as a mixture of cis- and trans-isomers which separated and characterized. Cis-[Pt(MeCN)₂Cl₂] has been synthesized using a well known technique of K₂[PtCl₄] interaction with acetonitrile in water. Heating cis-[Pt(RCN)₂Cl₂] (R = Me, CH₂Ph, CH₂CO₂Et) in the solid phase leads to cis-trans isomerization. In case of cis-[Pt(PhCN)₂Cl₂] thermal conversion results in trans-[Pt(PhCN)₂Cl₂] but the process of geometrical isomerizations accompained by a considerable decomposition of starting material and/or final products. Boiling of cis-[Pt(PhCH₂CN₂)Cl₂] in mixture of EtNO₂? PhCH₂CN or cis-[Pt(EtCO₂CH₂CN)₂Cl₂] in MeNO₂ or EtNO₂ solutions results in complete cis-trans conversion. Similarily heating of cis-[Pt(RCN)₂Cl₂] (R = Me, Ph) in solution produces an equilibrium mixture of cis- and transisomers.     

单N-乙酸取代O_2N_2大环配体及其稀土配合物的合成与表征

近年来,带电离官能团取代的大环成为大环化学研究的热点之一 [1～ 3]。这类大环除了环的腔径及环上配位原子种类对不同离子具有配位选择性外,其电离官能团的酸碱效应,也产生对 pH敏感的配位选择性。另外,由于大环骨架的相对刚性,刚柔相济的作用还起到提高配位能力,改进选择性的效果。迄今为止,人们对全氮取代的氮杂大环及其配合物作了相当深入的研究 [4～ 6],部分氮取代的氮氧杂大环及其配合物的研究还很少 [7,8]。从研究配体配位性能的观点来看,改变大环上氮取代的电离官能团数目可以进一步开发出具有良好选择性的配体。本文报道…