镧与β-丙氨酸配合物{[La_2(β-ala)_6(H_2O)_4](ClO_4)_6·H_2O}_n的合成及晶体结构

稀土在羊毛染色剂中用做助染剂犤１犦，在钙蛋白中用做钙离子的探针犤２犦得到广泛的应用，稀土的生物效应是以其与各种生物配体如氨基酸、肽、蛋白质、核酸等生物分子的作用为基础的，因此研究稀土氨基酸配合物的单晶结构对于探讨稀土离子与生物体的作用很有意义，稀土与有关α－丙氨酸的摩尔比为１∶１犤３～４犦和１∶２犤５～７犦类型的配合物的单晶结构已有报道，而有关稀土β－丙氨酸配合物的研究还很少犤８犦，特别是关于稀土β－丙氨酸配合物的单晶结构还未见报道，本文合成了高氯酸镧与β－丙氨酸的１∶３型的配合物，并测定了其晶…     

[Ni(en)_3]_4[HV~(Ⅳ)_(12)V~Ⅴ_6O_(42)(PO_4)]复合物的合成及晶体结构

金属－氧簇合物不仅在许多均相和异相的反应中有潜在的应用，而且还有可能形成一些特殊功能的材料，已经引起了从事生物无机和磁化学等科学家的兴趣犤１，２犦。其中具有球壳形结构的狖V１８O４２狚，通式为MX犤HYV１８O４２（E）犦的簇合物在国内外已有一些报道，如（N２H５）２犤Zn３V１８O４２（SO４）（H２O）１２犦·２４H２O犤３犦，狖犤Cu（１，２－pn）２犦４犤V１８O４２（H２O）犦狚·８nH２O犤４犦，其中由于还原程度的不同，狖V１８O４２狚的钒的混合价态组成有多种多样。在已见报道中金属离子M主要是碱金属和碱土…     

硝酸钐/硝酸镝/硝酸铒与组氨酸液-液反应的热动力学

稀土氨基酸配合物具有消炎、杀菌、降血糖等作用犤１犦。它们的晶体结构和相化学已有报道犤２，３犦。前报犤４犦曾详细报道了稀土硝酸盐与组氨酸配合行为的溶解度图和制备与表征。但文献中未见有关该类配合反应热动力学研究的报道。本文用微量热法对硝酸钐／硝酸镝／硝酸铒与组氨酸的液－液反应进行了热动力学研究。其结果可为这类配合物的反应机理研究和制备提供必要的技术参数。１实验部分１．１试剂RE（NO３）３·６H２O（RE＝Sm，Dy，Er）按文献犤５犦的方法制备。L－α－组氨酸为B．R．（上海康达氨基酸厂）；纯度＞９９．５％…     

一种二帽pseudo-Keggin结构簇合物[HN(C_2H_5)_3]_3[N(C_2H_5)_3]_2[Mo_8~ⅣMo_4~ⅤV_2~ⅣO_(38)(PO_4)]的水热合成、结构和性质研究

金属－氧簇合物因其结构多样性及在催化、材料和医药等方面的应用而引起人们的关注犤１犦。在众多金属－氧簇合物中，Keggin结构及金属取代Keggin结构金属－氧簇被大量报道，但由于很难获得高质量单晶，有关二帽Keggin结构的报道非常少，目前只有几例报道犤２～９犦。近年来，随着水热法应用到金属－氧簇的合成，陆续获得了一系列具有新颖结构的簇合物。１９９８年，通过水热法获得了第一个二帽pseudo－Keggin结构簇合物犤NH４犦４H犤PMo８VⅣ４VⅤ２O４２犦·２４H２O犤１０犦。我们用水热法以三乙胺做模板剂获得了一种全新的二帽pse…     

两个β-二酮Co(Ⅱ)配合物[Co(β-diketonate)2(py)2]的合成和晶体结构

钴是生物学上重要的微量元素，它能在一些酶中代替锌，而不改变原来酶的活性犤１犦，钴的光谱和磁性是酶活性部位的有效探针犤２犦。钴催化剂是单活性中心催化剂犤３犦，同时又是很好的乙烯齐聚催化剂犤４，５犦。β－二酮是重要的催化剂原料，徐德民等犤６犦报道了含有β－二酮金属配合物催化剂制备间规聚苯乙烯与聚丙烯共混复合物。宓霞等犤７犦报道了含β－二酮钛非茂催化剂催化降冰片烯聚合。近年来，已报道了一些β－二酮的Co?配合物犤８～１０犦的晶体结构，本文报道两个β－二酮的Co?配合物的合成和晶体结构。１实验部分１．１配合…     

天然及非天然氨基酸席夫碱锌配合物的合成与表征

氨基酸席夫碱及其金属配合物具有良好的抗菌、抗癌活性犤１,２犦,对其深入研究不仅对生物无机化学而且对医药均有重要意义。天然氨基酸席夫碱与过渡金属及稀土配合物的报道较多犤４～８犦,一些非天然氨基酸具有非常重要的生物功能,而非天然氨基酸及蛋氨酸席夫碱配合物报道较少犤９,１０犦,γ－氨基丁酸席夫碱配合物尚未见报道,也未见用X射线粉末衍射数据指标化来研究其晶体结构。锌是非常重要的必需微量元素,我们合成了β－丙氨酸、γ－氨基丁酸、DL－蛋氨酸水杨醛席夫碱与锌?的三种新配合物ZnL·nH２O（L＝sal－β－ala、sal－…     

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…     

四苯基卟啉氧合配合物的室温固相合成、表征及氧合性能

采用固相反应合成了四苯基卟啉与Fe2 、Co2 的配合物.在室温下,将其与分子O2作用,提纯后得到两种固态氧合配合物.通过元素分析、红外光谱、核磁共振氢谱、电导、热分析(TG/DTA)、紫外光谱等测试手段确定了氧合配合物的组成为[Co·TPP·O2](NO3):·2H2O、[Fe·TPP·O2]Cl2·2H2O,可知1mol配合物吸收了1mol O2.采用失重法测定了氧合配合物中的配位氧,确定1mol金属配合物吸收1mol O2形成超氧配合物.     

K10H3[Gd(SiMo4W7O39)2]配合物界面扩渗Ce和Lu及其介导性能

多金属氧酸盐由于具有独特的化学结构，作为特殊性能的功能材料已引起关注犤１～３犦。但其导电性和磁性差别较大，如何提高其导电性和磁性，进而制备出一类新型导电性和磁性材料，人们进行了探索。据文献报道犤４～６犦，多金属氧酸盐均是高质子导体，且电导率多数小于１０－３S·cm－１，并随温度的升高，导电性降低，很难作为固体电解质在氢－氧燃料电池等器件上应用。本文从相关基础理论入手，采用气相法，首次研究了Ce，Lu通过固－气界面反应对K１０H３犤Gd（SiMo４W７O３９）２犦多金属氧酸盐簇合物的化学热扩渗。利用ICP，IR，…     

不同双/多齿配体Co(Ⅱ)配合物的氧合性能

在室温水溶液体系中采用紫外-可见分光光度法和氧电极法对比研究了α-氨基酸(N/O型)、α-氨基醇(N/O型)、羟基多元羧酸(O/O型)和多胺(N/N型)这4类不同双/多齿配体的Co(Ⅱ)配合物的氧合性能及其氧合反应的可逆性.结果表明, O/O型含羟基的羧酸Co(Ⅱ)配合物无氧合性能; N/N型多胺Co(Ⅱ)配合物有强吸氧性, 但氧合反应不可逆; N/O型配体的Co(Ⅱ)配合物的氧合性能差异较大, 其中α-氨基酸Co(Ⅱ)配合物具有明显的可逆氧合性能, 而含1个—OH的α-氨基醇Co(Ⅱ)配合物没有吸氧能力, 含有2个—OH的α-氨基醇Co(Ⅱ)配合物有微弱的吸氧能力但氧合反应不可逆.分析探讨了N/O型配体中—OH和—COOH对Co(Ⅱ)配合物可逆吸氧性能影响的机理, 根据实验结果初步认为α-氨基酸配位结构是Co(Ⅱ)配合物具有可逆吸氧性能的基本配位结构单元.     

Chelating Behaviour of Substituted 3-4 Aryl-Hydrazo-Pentane-2, 4-Dione: Part VI. Potentiometric and Infrared Studies of the Ligands and Their Divalent Metal Complexes

The dissociation constants of 3-phenylhydrazo-pentane-2, 4-dione and its o-, m-, p-carboxy derivatives, and the stability constants of complexes of divalent metal ions with the o-carboxy derivative are determined by pH-metric method. The ir-spectra of the ligands and some divalent metal complexes with the o-derivative are discussed.     

Solution Properties of Aluminum and Titanium Complexes with o-Chlorophenylfluorone and Competition Coordination for Selective Determination of Trace Amounts of Titanium

 The competition coordination for selective determination (CCSD) is described and the complexations of Ti(IV) and Al(III) with o-chlorophenylfluorone (o-CPF) is studied at pH 4.5 in presence of Triton X-100. The determination of equilibrium constants of the complexes was made by the spectral correction technique in place of ordinary spectrophotometry. The complexes are formed as [Al(o-CPF)₃]³⁻ and [Ti(o-CPF)₃]²⁻ and their stepwise and cumulative stability constants are calculated. Trace amounts of Ti can substitute Al from its o-CPF complex and the competition coordination has been used in the quantitative determination of Ti in water samples with satisfactory results. Received July 14, 2000. Revision June 25, 2001.     

The Synthesis,Characterization and Conductance Studies of New Cu(II), Ni(Ii) And Zn(II) Complexes with the Schiff Base Derived from 1,2-Bis-(o-Aminophenoxy)Ethane and Salicylaldehyde

Cu(II), Ni(II) and Zn(II) complexes with the Schiff base derived from 1,2-bis-(o-aminophenoxy)ethane with salicylaldehyde have been prepared. The complexes have been characterized by elemental analysis, magnetic measurements, ¹H NMR, ¹³C NMR, UV, visible and IR spectra as well as conductance measurements. The ligand is coordinated to the central metal as a tetradentate ONNO ligand. The four bonding sites are the central azomethine nitrogen and aldehydic OH groups. The ligand was used for complexation studies. Stability constants were measured by a conductometric method. Furthermore, the stability constants for complexation between ZnCl₂ and Cu(NO₃)₂ salts and N,N′-bis(salicylidene)-1,2-bis-(o-aminophenoxy)ethane (H₂L) in 80% dioxane/water and pure methanol were determined from conductance measurements. The magnitudes of these ion association constants are related to the nature of the solvation of the cation and the complexed cation. The mobilities of the complexes are also dependent, in part, upon solvation effects.     

Potentiometric and Conductometric Studies on the Complexes of Some Rare Earth Metals with Rhodanine Azosulfonamide Derivatives, XII

Stability constants for La³⁺, Ce³⁺, UO₂ ²⁺, and Th⁴⁺ metal ion complexes with rhodanine azosulfonamide derivatives have been determined potentiometrically in 0.1 M KCl in a 30% (v/v) ethanol–water mixture. The order of the stability constants of the complexes found was to La³⁺ < Ce ²⁺ < UO ₂ ²⁺ < Th ⁴⁺. The influence of substituents on the stability of the complexes was examined on the basis of electron-repelling property of the substituent. The effect of temperature on the stability constants was studied and the Gibbs energy, the enthalpy, and entropy of complexation thermodynamic parameters were derived and are discussed. The stoichiometries of these complexes were determined conductometrically and the results indicated the formation of 1:1 and 1:2 (metal:ligand) complexes.     

Crown Ether Complexes of Six-Membered N-heteroaromatic Cations

Crown ether complexes of six-membered N-heteroaromatic cations and the closely related bicyclic purinium cation (6) have been studied by ¹H NMR, mass spectrometric and crystallographic methods. The stability constants for the complexes were determined by ¹H NMR titration in acetonitrile solution and the complexation stoichiometry by ¹H NMR and ESI mass spectrometric methods. Altogether six crystal structures of complexes were determined to study the complexation in the solid state. Hydrogen bonding was observed to be the most important interaction for the complexation both in solution and in the solid state but – interactions also contribute to it. All crystal structures of the DB18C6 complexes with six-membered N-heteroaromatic cations, except for 4-hydroxypyridinium, are isomorphous to previously studied five-membered N-heteroaromatic cations and pyridinium complexes. Such a close resemblance is not observed in B18C6 and 18C6 complexes or DB18C6purinium (6).     

Coordinating Properties of Co(II) and Zn(II) Complexes with Sterically Hindered Porphyrins

Cobalt(II) and zinc(II) complexes with 5,15-di(o-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetra-n-buthylporphyrin and its capped analogues, where the MN₄ reaction site is shielded by bridging groups containing m-phenylene and dimethoxy-substitutedp-phenylene fragments, were synthesized. Equilibrium constants of additional coordination of pyridine and N-methylimidazole by these metalloporphyrins were determined at 298 K. It was found that steric distortion of the porphyrin core destabilizes extra complexes.     

Stability Constants of Some Divalent Complexes of m- and p-Phenylenediamine Tetraacetic Acid

The dissociation constants of m-, and p-phenylenediaminetetraacetic acid (m-, and p-, PDTA) have been determined potentiometrically at room temperature (about 25°C) in an ionic strength of 0.10 M KNO₃. The stability constatns of their metal complexes have also been determined by UV spectroscopic, potentiometric, and polarographic methods. The formula of the metal complexes by spectroscopic and polarographic methods are both in good agreement to be 1:1. The order of the stability of the metal complexes is: Cu>Ni>Zn>Co>Cd>Mg, Ca, Ba, Sr. Which is in accordance with Irving-William stability order.     

Potentiometric Studies on SomeCephalosporin Complexes

Summary.  The interaction of Ca(II), Cu(II), Zn(II), Pb(II), and La(III) ions with the antibiotics cephalexin, cefadroxil, cephaloridine, and cefoperazone as secondary ligands was investigated potentiometrically. The formation constants were determined for a ligand-to-metal ratio of 1:1 at 25°C and KNO₃. The protonation constants of the complexes were evaluated for the system . The order of stability of the binary and ternary complexes were examined. It was found that glycine adds preferably [M(II)-cephalosporin] rather than to the aqueous complexes of M(II). In all cases 1:1:1 complexes were formed. Received February 4, 2000. Accepted (revised) May 10, 2000     

Complexes of pyrimidine DNA bases with thallium(I)

The stability constants of complexes of a thallium(I) ion with cytosine and thymine were determined in aqueous solution at 25°C and 0.1 mol dm⁻³ ionic media, using a combination of potentiometric and spectrophotometric techniques. Sodium perchlorate was used to maintain the ionic strength. The composition of the formed complexes was determined and it was shown that thallium(I) forms two mononuclear 1:1 species with cytosine of the type TIHL⁺ and TIL, and a mononuclear 1:1 complex species with thymine in the form TIHL, in the pH range of study (1–11), where L represents the fully dissociated ligand. The cumulative stability constants, β _xyz, of the complexes, [(thallium)_x(H)_y(ligand)_z], were calculated by a nonlinear fitting method and their distributions were presented as a function of-log[H⁺]. This text was submitted by the authors in English.     

Study of Electron Donor–Acceptor Complex Formation of o-Chloranil With a Series of Phosphine Oxides and Tri- n-butyl Phosphate by the Absorption Spectrometric Method

Electron donor–acceptor (EDA) complex formation of o-chloranil with six different phosphine oxides and tri-n-butyl phosphate (TBP) has been studied in CCl ₄ solution by the UV-VIS absorption spectrophotometric technique. An absorption band due to a charge–transfer (CT) transition is observed in the visible region. Utilizing the CT transition energy, the electron affinity of o-chloranil in solution has been calculated. Degrees of charge transfer, and oscillator and transition dipole strengths have also been calculated for all of the investigated EDA complexes. Except for TBP, other phosphine oxides, viz., tri-n-octyl phosphine oxide, tri-n-butyl phosphine oxide, triphenyl phosphine, octyl(phenyl)-N,N-diisobutylcarbamoylphosphine oxide, octyl(phenyl)-N,N-dicyclohexylcarbamoylmethylphosphine oxide and octyl(phenyl)-N,N-diisopropylcarbamoylmethylphosphine oxide have been shown to form stable 1:1 EDA complexes with o-chloranil. The complex of TBP with o-chloranil decays slowly into a secondary product. Formation constants of the EDA complexes have been determined.