Electrochemical Studies of Eight New Divalent Transition Metal Benzenesulphonate Ternary Complexes with 1,10-Phenanthroline

The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1, 10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltammetry(CV). Based on the CV data the influences of various coordination modes on the electrochemical behavior of the complexes were discussed. The diffusion coefficient Dc and rate constant k, of those complexes in DMF systems were estimated according to CV and the results show that these processes were all quasi-reversible.     

Determination of Stability Constants of Copper(I) Chelates with 1,10-Phenanthroline by Thermal Lensing

Using investigations of the copper(I)–1,10-phenanthroline system as an example, it is shown that thermal lensing can be used for determining stability constants at a level of concentrations one–two orders of magnitude lower compared to conventional spectrophotometry, with better precision of measurements. The values of stability constants are log₂= 11.7 ± 0.7 without regard for stepwise chelation, and logK ₁= 5.9 ± 0.3, logK ₂= 5.4 ± 0.3, and log₂= 11.3 ± 0.6 taking into account stepwise chelation. It is shown that, when shifting from microgram to nanogram amounts of reactants in the determination of stability constants by thermal lensing, changes in the kinetic parameters of the reaction studied should be taken into account. The thermal-lens limit of detection of copper(I) is 2 × 10^–8M; the linear calibration range is 4 × 10^–8–2 × 10^–5M (488.0 nm, pump power 120 mW). The data obtained were used for determining copper(I) in the hydrogen sulfide layer of the Baltic Sea.     

Synthesis and Spectroscopic Characteriration of Transition MetalComplexes of Maleionitriledithiolene and 1,10-Phenanthroline

Thedithiolenesanddiiminesandtheirmetalcomplexesareanimportantresearchfieldintheorganicandcoordinationchemistry'-'.Metalcomplexesofadithioleneandadiiminehaveexcellentelectronicfullctionsduetotheintramolecularchargetransferfromaligandtootherligand(LL'C...     

四硫富瓦烯四硫纶桥联金属邻菲啰啉配合物的合成与性质

以2,3,6,7-四(2’-氰乙硫基)四硫富瓦烯为桥配体的前驱物, 合成了标题配合物μ-(ttftt)-[M(phen)]2 (M＝MnII, FeII, CoII, NiII, CuII, ZnII). 配合物的结构和性质经由元素分析、核磁共振波谱、红外光谱、紫外-可见光谱、荧光光谱、摩尔电导率和量子化学计算表征, 研究了电氧化还原和对Li/SOCl2电池的催化特性. 发现铁和钴配合物具有较高的催化活性且有利于电池的大电流和低温放电, 在25 ℃和电流密度25 mA/cm2条件下铁配合物使电池的电压和容量分别提高了133 mV和218 mAh.     

四硫富瓦烯四硫纶桥联金属邻菲哕啉配合物的合成与性质

以2,3,6,7-四(2'-氰乙硫基)四硫富瓦烯为桥配体的前驱物,合成了标题配合物μ-(trftt)-[M(phert)]2(M=MnⅡ,FeⅡ,CoⅡ,NiⅡ,CuⅡ,ZnⅡ).配合物的结构和性质经由元素分析、核磁共振波谱、红外光谱、紫外-可见光谱、荧光光谱、摩尔电导率和量子化学计算表征,研究了电氧化还原和对Li/SOCl2电池的催化特性.发现铁和钴配合物具有较高的催化活性且有利于电池的大电流和低温放电,在25℃和电流密度25 mA/cm2条件下铁配合物使电池的电压和容量分别提高了133mV和218mAh.     

Mechanochemical Reaction of 1,10-Phenanthroline with Metallic Iron

Fe(II) complex is isolated from the products of mechanical activation of a mixture of the powdered carbonyl Fe and 1,10-phenanthroline. According to the data of elemental analysis, an electronic absorption spectra, magnetochemical and EPR studies, the isolated compound is [FePhen₃]²⁺ Phen^–OH^– · 3H₂O that contains Phen^– radical-anion.     

一水合邻菲罗啉的热化学性质

用纯度为99.999%的量热基准苯甲酸标定了实验室建立的精密转动弹量热计,其能当量为18604.99±8.14J/K,测得一水合邻菲罗啉(phen·H2O)的燃烧能为-5757.45±2.53kJ/mol,换算成标准燃烧焓为-5759.93±2.53kJ/mol,进而计算出一水合邻菲罗啉的标准生成焓为-391.34±2.98kJ/mol。     

Formation Thermodynamics of Binary and Ternary Lanthanide(III) Complexes with 1,10-Phenanthroline and Chloride in N,N-Dimethylformamide

Formation thermodynamics of binary and ternary lanthanide(III) (Ln = La, Ce, Nd, Eu, Gd, Dy, Tm, Lu) complexes with 1,10-phenanthroline (phen) and the chloride ion have been studied by titration calorimetry and spectrophotometry in N,N-dimethyl-formamide (DMF) containing 0.2 mol-dm^–3 (C₂H₅)₄NClO₄ as a constant ionic medium at 25°C. In the binary system with 1,10-phenanthroline, the Ln(phen)³⁺ complex is formed for all the lanthanide(III) ions examined. The reaction enthalpy and entropy values for the formation of Ln(phen)³⁺ decrease in the order La > Ce > Nd, then increase in the order Nd < Eu < Gd < Dy, and again decrease in the order Dy > Tm > Lu. The variation is explained in terms of the coordination structure of Ln(phen)³⁺ that changes from eight to seven coordination with decreasing ionic radius of the metal ion. In the ternary Ln³⁺-Cl^–-phen system, the formation of LnCl(phen)²⁺, LnCl₂(phen)⁺, and LnCl₃(phen) was established for cerium(III), neodymium(III), and thulium(III), and their formation constants, enthalpies, and entropies were obtained. The enthalpy and entropy values are also discussed from the structural point of view.     

Trinuclear Metal Complexes Based on 1,10-Phenanthroline Derivates as Catalysts for Cleavage of a RNA-Model Substrate

Two multidentate ligands 2,9-di[6'-(2″-hydroxyl-3″-methoxyphenyl)-n-2',5'-diazahexyl]-1,10-phenanthroline(LA)and 2,9-di(6'-α-phenol-n-2',5'-diazahexyl)-1,10-phenanthroline(LB)were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu(Ⅱ)and Zn(Ⅱ)] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate(HPNP).The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.     

氯化钴/邻菲罗啉催化氯苄双羰化合成苯丙酮酸的研究

双羰化是制备α-酮酸及其衍生物的重要反应 ,因其反应途径简捷且收率高而倍受青睐 ,国内外有不少关于氯苄双羰化合成苯丙酮酸的报道 .1 982年发现的钯配合物主要用于催化芳基卤代物的双羰化 [1] ;金子林等[2 ] 进行了八羰基二钴催化氯苄双羰化合成苯丙酮酸的研究 ,李光兴等[3 ] 近期也报道了吡啶 - 2 -羧酸钴的催化氯苄高效合成苯丙酮酸 .受前期吡啶 - 2 -羧酸钴催化双羰化研究成果的启发 ,我们进一步探讨了不同的席夫碱与氯化钴组成的催化体系的双羰化性能 .实验发现 ,采用“一锅煮”的方式 ,将氯化钴和邻菲罗啉 ( Phen)按一定比例加入到…     

1,10-邻菲咯啉衍生物的合成及其晶体结构

以1,10-邻菲咯啉为原料,经氧化反应合成了1,10-邻菲咯啉-5,6-二酮(1);1与对氟苯甲醛反应合成了2-苯基(4-氟)-咪唑[4,5]-1,10-邻啡咯啉(2).1和2的结构经1H NMR,MS和X-射线单晶衍射表征.1为正交晶系,Pna21空间群,晶胞参数为:a=14.329 0(4)(A),b=12.370 0(3)(A),c=6.395 6(16)(A),α=90°,β=90°,γ=90°,V=1 133.5(5)(A)~3,Z=14,Dc=2.521 g·cm~(-3),μ=12.430 mm~(-1),F(000)=789,最终偏离因子R=0.039 8,wR=0.114 7.2为单斜晶系,P21/n,空间群晶胞参数为:a=9.810 0(4)(A),b=10.951 0(4)(A),c=17.3670(7)(A),α=90.000°,β=99.042(5)°,γ=90.000°,V=1 842.5(12)(A)~3,Z=4,Dc=1.292 g·cm~(-3),μ=0.095mm~(-1),F(000)=732,最终偏离因子R=0.091 2,wR=0.334 9.     

Structure and Reactivity of the 1,10-Phenanthroline Complex with Nitrenium Cation

According to the X-ray diffraction data, the cationic fragment in 1-amino-1,10-phenanthrolinium mesitylenesulfonate is a unidentate n-complex whose asymmetric structure is retained in solution. Quantum-chemical calculations by the AM1 method and ab initio (6-31G, 6-31G*, MP2/6-31G) give geometric parameters of the cation, which are similar to those determined experimentally. No dynamic processes involving intra- or intermolecular transfer of the NH2 group was observed up to 100°C by NMR spectroscopy. 1-Amino-1,10-phenanthrolinium cation does not react with 4-methylpyridine and 4-methyl-1,10-phenan-throline with transfer of the amino group, and it fails to react with mesitylene and anthracene at elevated temperature.     

Structure and Thermal Properties of Transition Metal Imidazole Chloride

1 INTRODUCTION Imidazole is of considerable interest as a ligand in many biological systems, in which it provides a potential binding site for the metal ions[1]. Imidazole itself is a unidentate ligand and forms complexes with the metal ions through its tertiary nitrogen atoms. It has been reported that a large number of imidazole derivatives possess diverse pharmaco- logical effects, including antiinflammatory, antimi- crobial, antimalarial and antitumor activities[2]. To our knowledge…     

Concave Reagents 36: Transition Metal Complexes With Concave 1,10-phenanthrolines

Complexes between concave 1,10-phenanthrolines 1 and transition metal ions (Mn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Ag + , Cd 2+ ) have been synthesized and characterized by various methods including UV titration, NMR spectroscopy, EPR spectroscopy, cyclovoltammetry, microanalysis and X-ray analysis. The concave 1,10-phenanthrolines 1 form 1:1 complexes with the metal ions while the complexes of analogous, but non-bimacrocyclic 1,10-phenanthrolines such as 2 and 2,9-dimethyl-1,10-phenanthroline exist in varying stoichiometries.     

Molecular and Crystal Structure of 1,10-Phenanthroline Complex with Nitrosonium Cation

1,10-Nitroso-1,10-phenanthrolinium tetrafluoroborate was subjected to X-ray diffraction analysis. A distinctive feature of the complex is the NO group position between two nitrogen atoms of the phenanthroline skeleton, and so the complex may be regarded as belonging to bidentate type. The distance from the N atom of the group to the nitrogens of the skeleton are approximately equal (2.3 Å) and are considerably shorter that the average intermolecular contacts of the pair of nitrogen atoms N...N (3.0 Å). In the crystal two types of cations are present where the NO groups are oriented at angles 54 and 61° with respect to phenanthroline skeleton, and the length of N-O bonds is close to that in NO⁺ cation. The geometrical parameters of cation obtained by ab initio calculations are close to experimental data.     

Cinnamoylacetanilides and Their Metal Chelates

A new series of β-ketoanilides, in which the keto group attached to an olefinic linkage, have been synthesized by the reaction of acetoacetanilide with p-substituted benzaldehydes (4-methoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-dimethylaminobenzaldehyde and 4-nitrobenzaldehyde) under specified conditions. The existence of these β-ketoanilides predominantly in the intramolecularly hydrogen bonded enol forms has been well demonstrated from their IR, ¹H NMR and mass spectral data. Details on the formation of [ML₂] complexes of these compounds with Ni(II), Cu(II) and Zn(II) and their nature of bonding were discussed on the basis of analytical, IR, ¹H NMR and mass spectral data.     

盐酸胍中微量铁的光度测定

本文考察了盐酸胍对邻菲口罗啉光度法测定微量铁的实验条件的影响，并建立了邻菲口罗啉分光光度法直接测定盐酸胍中微量铁含量的方法。当盐酸胍中铁含量为5μg／g时，相对标准偏差为2％。