[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究

The two symmetrical isomers in [Co(amp)₂Cl₂]₂[ZnCl₄](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me₂SO-d₆ with the central peak of the CD₃ septet as the reference ( ₁₃C,δ 39.37; ₁H,δ 2.49 relative to SiMe₄). Cation exchange media used was Dowex 50Wx 2(H⁺ form, 200～400mesh; Biorad).     

Spectrophotometric determination of ciprofloxacin in pure form and in tablets through charge-transfer complexation reactions

Three simple, quick and sensitive spectrophotometric methods are described for the determination of ciprofloxacin. The methods are based on the reaction of this drug as ann-electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 7,7,8,8,-tetracyanoquinodimethane (TCNQ) andp-chloranil (CL) as -acceptors to give highly coloured complex species. The coloured products are quantitated spectrophotometrically at 460, 843 and 550 nm for DDQ, TCNQ and CL, respectively. Optimization of the different experimental conditions is described. Beer's law is obeyed in the concentration ranges 5–50, 1.5–15 and 20–200 g ml^–1 ciprofloxacin, but the concentration ranges for best accuracy are 10–48, 2.5–15 and 35– 195 g ml^–1 of drug for DDQ, TCNQ and CL, respectively. The relative standard deviations are less than 1.5%. Applications of the suggested methods to ciprofloxacin tablets are presented and compared with the USP method. The stability constants of the 11 DDQ and CL complexes were 1.086 × 10⁴ and 2.581 × 10⁴ lmol^–1, respectively, whereas for the 12 TCNQ complex it was 3.62 × 10⁸1. mol^–1.     

手性奎宁-卟啉锰催化剂的合成及其催化性能

为了寻找催化活性、相转移活性和手性诱导为一体的卟啉配体[1-4],我们把卟啉和手性相转移源连结起来,用奎宁-卟啉化合物作配体[5],考察其锰 配合物为催化剂对烯烃环氧化反应的催化性能。奎宁-卟啉锰 配合物结构式如下:1　实验部分1.1　试剂和仪器苯乙烯和α-甲基苯乙烯在氮气保护下减压蒸馏处理。氧源ＮａＯＣｌ的浓度由碘量法测定。其余试剂均为化学纯,色谱标样环氧苯乙烯和α-甲基环氧苯乙烯按文献[6]方法合成。奎宁-卟啉配体按文献[5]合成。260-50型红外光谱仪,ＫＢｒ压片;ＵＶ-3000型紫外可见光谱仪,溶剂ＤＭＦ;ＭＴ-3型ＣＨＮ元素…     

Bestimmung von Gleichgewichtskonstanten für Ligandenaustauschreaktionen von [TcNX4]− (X = Cl,Br) mit Hilfe der EPR

Polynuclear Complexes with Fe? As, Fe? Sb, and Fe? Bi Frameworks The anionic iron clusters Fe₃(CO)₁₁^2? and Fe₄(CO)₁₃^2? were reacted with compounds EX₃ and with organic derivatives REX₂ and R₂EX of the elements arsenic, antimony, and bismuth. Commonly redox and cluster degradation reactions were observed. The new complexes [(CO)₄Fe? AsMe₂? Fe(CO)₄]^?, [HFe₃(CO)₉(mu;₃-SbBu^t)]^?, [Fe₃(CO)₁₀ (mu;₃-Sb)]^?, and [Fe₃(CO)₁₀(mu;₃-Bi)]^? were formed and isolated as their PPN salts. The Fe? As? Fe complex was identified by a structure determination, the other complexes were identified by their spectra.     

Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).     

钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用

用pH-电位滴定法测定了Pd(L)(Aa)⁺三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO₃)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。     

meso-四(邻烷氧基苯基)卟啉合钴的合成、表征和性能研究

合成了meso-四(邻烷氧基苯基)卟啉合钴配合物10个,其中未见文献报道的新化合物8个，研究了其合成、分离、纯化方法,首次得到了该系列化合物的晶体或固体。用¹H NMR、MS、IR、UV、元素分析等表征确证了其结构,报道和解析了该类卟啉钴配合物的¹H NMR特殊波谱现象。用差示扫描量热法(DSC)和偏光显微镜(PM)研究了该系列配合物的液晶性能,发现6个配合物具有液晶性。研究了烷氧基链长、金属离子和分子空间结构对卟啉液晶性能的影响,烷氧基链长的增加、金属配合物的形成有利于液晶性能的改善。     

Hydrothermal synthesis, crystal structures and luminescent properties of two new Ln(III)–succinate (Ln=Eu, Tb) complexes exhibiting three dimensional networks

Two new coordination polymers, [Eu₂(L)₃(H₂O)₂]_n 1 and {[Tb₂(L)₃(H₂O)₂]·H₂O}_n 2, (H₂L=succinic acid) have been synthesized by the reaction of H₂L with nitrate salts of Eu(III) or Tb(III) under hydrothermal conditions. The X-ray diffraction analysis reveals that the two complexes are constructed by L bridging the chains of edge-sharing EuO₈(H₂O) or TbO₈(H₂O) polyhedra to form 3D network structure. 1 and 2 possess different topological structures due to the difference in the conformations of L. The solid photoluminescence of 1 and 2 was also investigated in room temperature.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.