多核配合物中金属间相互作用的电化学研究：取代三联吡？…

报道了２个取代三联吡啶配体（４′－苯基－２，２′：６′，２″－三联吡啶（Ｌ１）和４′－二茂铁基－２，２′：６′，２″－三联吡啶（Ｌ２）的Ｃｏ（Ⅱ）配合物（Ｃｏ（Ⅱ）（Ｌ１）２）（ＣｌＯ４）２．４ＣＨ３ＣＮ（１）和（Ｃｏ（Ⅱ）（Ｌ２）２）（ＣｌＯ４）２Ｈ２Ｏ（２）的合成及配体Ｌ２的配合物１和配合物２的晶体结构，电化学研究表明：在配合物２中，由于Ｃｏ＾２＋的作用，二茂铁基的氧化电位较配体Ｌ２中的二茂铁     

新试剂（MSBTAMB）双波长光度法测定微量铜（II）的研究

研究了新试剂２－〔２＇－（６＇－甲磺酰－苯并噻唑）偶氮〕－５－二甲氨基苯甲酸（ＭＳＢＴＡＭＢ）与铜（Ⅱ）的显色反应。试验表明，在ｐＨ２．０￣５．１和４０％乙醇介质中，Ｃｕ（Ⅱ）与ＭＳＢＴＡＭＢ形成１＋１稳定的配合物，其最大吸收波长为６４２ｎｍ，用单波长法测得配合物的Σ６４２＝６．７４×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，双波长法测得的Σ６４２．５４６＝１．０９×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－     

二茂金属共轭大环配体配合物的结构及性质

报道了配体Ｎ－（二茂铁基甲基）－１,４,７－氮杂－９－冠－３（Ｌ１）和Ｎ－（二茂钌基甲基）－１,４,７－氮杂－９－冠－３（Ｌ２）的Ｃｏ（Ⅲ）和Ｆｅ（Ⅲ）配合物１－４的合成及电化学性质,配合物「Ｃｏ（Ⅲ）（Ｌ１）２（ＡｃＯ）２（ＯＨ）」（ＣｌＯ４）（Ｉ）２（１）的晶体结构显示这些配合物具有线型排列的四金属中心结构,电化学研究表明：在这些配合物中,客体金属离子通过分子片断的电子传递作用使二茂金属的金属     

镍（Ⅱ）与2—（5—溴—2—吡啶偶氮）—5—二甲氨基苯胺显色反应的研究及铝合…

本研究了新显色剂２－（５－溴－２－吡啶偶氨）－５－二甲氨基苯胺与镍（Ⅱ）的反应条件。试验结果发现，在阴离子表面活性剂十二烷基硫酸钠存在下，在ｐＨ５．２～６．５范围内，试剂与镍（Ⅱ）形成稳定的２：１配合物。其最大吸收波长在５７０ｎｍ处，表观摩尔吸光系数为１．２４×１０＾５Ｌ．ｍｏｌ＾－１。镍（Ⅱ）浓度在０～０．４μｇ．ｍＬ＾－１之间符合比尔定律。以硫脲和氟化铵作掩蔽剂，可消除Ｃｕ＾２＋，Ｐｄ＾２＋     

M（Ⅱ）（ATP）^2—与核酸碱基（腺嘌呤,胞嘧啶）三元混配配…

用ＰＨ电位滴定法测定 篱子（Ｍ＾２＋＝Ｃｕ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＝，Ｚｎ＾２＋，Ｃｄ＾２＋）与核酸碱基（Ｐ＝腺嘌呤，胞嘧啶）形成的二夫配合物以及与腺甘－５＇－三酸（ＡＴＰ）形成的三元混配配合物的稳定常数，三元配合物相对于二元酚物的稳定性用平衡常数ΔｌｇＫＭ大，这可能与三元混配配合物分子内存在配体间的芳环堆积、氢键作用以及πＡ－πＢ协同效应有关。     

2, 6─二甲酸─4─取代苯酚双缩苯甲酰肼双核铜(Ⅱ)配合物的合成与磁性

本文合成并表征了两个新的双核铜（Ⅱ）配合物：［Ｃｕ２（Ｌ）（μ－Ｃｌ）Ｃｌ２］，配体Ｌ为２，６－二甲酰－４－基苯酚双缩苯甲酰肼，取代基分别为氯（Ｌ１）和叔丁基（Ｌ２）。配合物具有相同的组成和配位构型。变温磁化率测定结果表明，由于取代基不同，其磁交换参数分别为－４６．２ｃｍ＾－１（Ｌ１）和－５７．６ｃｍ＾－１（Ｌ２）。     

三核过渡金属配合物[M3^ⅢO（OOCR）6L3]^＋（M=Cr,Fe,Mn;R=CH3,C2H5,CH …

采用＾１Ｈ ＮＭＲ谱研究了通式为（Ｍ３＾ⅢＯ（ＯＯＣＲ）６Ｌ３）＾＋（Ｍ＝Ｃｒ,Ｆｅ,Ｍｎ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,ＣＨ２ＮＨ２;Ｌ＝Ｃ５Ｈ５Ｎ,Ｈ２Ｏ）的一系列氧心三核过渡金属配合物,主要考察其＾１Ｈ化学位移随金属、配体、温度、溶剂等因素变化而变化的规律。结果表明,骨架金属对化学位移的影响最大,Ｍ３Ｏ中的３个金属离子间存在反铁磁变换相互作用。对Ｍｎ配合物中顺磁中心对化学位移和线宽的影响机制的研究表     

乙酰基二茂铁2,6—吡啶二甲酰基腙的合成及其与Zn（Ⅱ）的配位行为

本文利用乙酰基二茂铁与２，６－吡啶二甲酰肼的缩合反应，首次合成了乙酰基二茂铁２，６－吡啶二甲酰基腙（Ｈ２Ｌ），在甲醇溶液中得到了它与醋酸锌的固态配合物，其组成为Ｚｎ２Ｌ（ＣＨ３ＣＯＯ）２．８Ｈ２Ｏ用摩尔比法测定了Ｈ２Ｌ与Ｚｎ（Ⅱ）的配位比，结果表明与固态配合物中Ｈ２Ｌ与Ｚｎ（Ⅱ）的配位比相吻合。     

某些有机硅及2—三丁基锡二茂铁衍生物的合成及表征

由Ｎ，Ｎ－二甲氨甲基二茂铁（Ｉ）单锂化后与三甲基氯硅烷（Ｍｅ３ＳｉＣｌ）反应，合成了２－（三甲硅基）二甲氨甲基二茂铁（Ⅱ）；Ⅱ再单锂化后与Ｍｅ３ＳｉＣｌ反应得到了２，５－二（三甲硅基）二甲氨甲基二茂铁（Ⅲ）；单锂化的Ｉ与Ｍｅ２ＳｉＣｌ２反是得到了双－（２－（二甲氨甲基）二茂铁基）二甲基硅烷（Ⅳ）双锂化Ｉ与二倍量的Ｍｅ３ＳｉＣｌ反应得到了２，１′－二（三甲硅基）二甲氨甲基二茂铁（Ｖ），由碘化（２－（     

[Fe（CN）6]^4—还原trans—[Co（en）2（ImH02]^3＋的电子转移反应 …

在不同的温度下，考察了六氰合铁配阴离子「Ｆｅ（ＣＮ）５」＾４－还原ｔｒａｎｓ－「Ｃｏ（ｅｎ）２（ＩｍＨ０２」＾３＋的反应动力学。结果表明，反应遵循Ｈ．Ｔａｕｂｅ所提出的外配位界电子传递机理。在２５℃，Ｉ＝０．５ｍｏｌ．Ｌ＾－１，ｔｒａｎｓ－「Ｃｏ（ｅｎ）２（ＩｍＨ）２」＾３＋／「Ｆｅ（ＣＮ）６」＾４－反应体系的前驱配合物离子对形成常数为Ｑ１ｐ＝９８．９ｍｏｌ＾－１．Ｌ，电子转移速率常数为Ｋｍ＝１．     

The Preparation of Dicompartmental Multifunctional Group Ligands

A convenient method for the preparation of the phenol-based ligands 1,6-bis(2-thiophenyl)-2,5-bis(2-hydroxy-3-hydroxymethyl-5-methylbenzyl)-2,5-diazahexane and 1,6-bis(5-methyl-2-thiophenyl)-2,5-bis(2-hydroxy-3-hydroxymethyl-5-methyl-benzyl)-2,5-diazahexane possessing two dissimilar compartments having multifunctional groups is reported. To synthesize these ligands, an equivalent of 1,6-bis(2-thiophene)-2,5-diazahexane or 1,6-bis(5-methyl-2-thiophene)-2,5-diazahexane and two equivalents of 2,2-dimethyl-6-methyl-8-(chloromethyl)benzo-1,3-dioxin were reacted in the presence of Na₂CO₃ in 1,4-dioxane, followed by acid hydrolysis of an acetonide-protecting group. Characterization data for the new compounds is reported.     

The synthesis and structural analysis of cis -β-{(1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane O(1,2-diazahexane))(1,2-benzoquinone diimine))ruthenium(II)} and related complexes

Several isomers are possible when N₄-tetradentate ligands coordinate to form metal complexes. Here we report the synthesis and structural analysis of cis-β-{[1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane)(1,2-benzoquinone diimine)]ruthenium(II)} formed exclusively from the β-precusor, β-{[1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane) (dimethylsulfoxide)chloride] ruthenium(II)} hexaflourophosphate. Ruthenium(II) complexes synthesised from 1,6-di(2′-pyridyl)-2,5-dibenzyl-2,5-diazahexane, produce only two isomers which can be separated by recrystallisation into α- and β-[Ru(picenbz₂)(dmso)Cl]PF₆ (where picenbz₂ is 1,6-di(2′-pyridyl)-2,5-dibenzyl-2,5-diazahexane). The distinctively different proton NMR spectra of the isomers are an especially convenient feature with which to assess separation. Isomeric structure of the precursor, α or β, is conserved upon coordination of a bidentate ligand, such as benzene-1,2-diamine, 4,5-dimethyl-benzene-1,2-diamine, naphthalene-2,3-diamine, 2,2′-bipyridine, 1,10-phenanthroline or dipyrido[3,2-d:2′3′-f] quinoxaline, to produce complexes of the type α- or β-[Ru(picenbz₂)(bidentate)](PF₆)₂. The synthesis, separation and characterisation of the α- and β-precursors and the α- and β-[Ru(picenbz₂)(bidentate)](PF₆)₂ complexes are reported. Moreover, the crystal structures have been determined for β-[Ru(picenbz₂)(dmso)Cl]PF₆.0.5H₂O (C₃₀H₃₇N₄O_1.5F₆PSClRu); it is triclinic, space group P 1, a?=?9.987, b?=?12.883, c?=?14.287?Å, α?=?72.11, β?=?78.65, γ?=?88.39° and Z?=?2 and β-[Ru(picenbz₂)(bqdi)](PF₆)₂, (C₃₄H₃₈N₆F₁₂P₂Ru) which is triclinic, space group P 1, with a?=?10.129, b?=?10.338, c?=?19.587?Å, α?=?104.42, β?=?93.36, γ?=?92.00° and Z?=?2. The structures were determined at room temperature and refined by least-squares methods to R?=?0.044 for 5109 and R?=?0.075 for 3057 non-zero diffractometer data, respectively, for the dmso and bqdi species above.     

Polyimides containing nonaromatic nitrogen linkages

Two diamines, 2,5-bis (4-aminophenyl)-2,5-diazahexane and 1,4-bis (4-aminophenyl)-1,4-diazacyclohexane were chosen as components for polyimidizations because they have melting points that differ by nearly 200°C (66–67 and 229–230°C, respectively) and are relatives of p-nitro-N,N-dimethylaniline. The melting points of the model compounds (phthalic anhydride) do not differ by as much as those of the free amines [303–304 and 386°C (DSC), respectively]. Six polyimides were prepared by a two-step polycondensation of the diamines with pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl) ethylidene] bis-1,3-isobenzofurandione. DSC thermograms failed to indicate any distinct transitions up to 450°C, however, the polyimide prepared from 2,5-bis (4-aminophenyl)-2,5-diazahexane and pyromellitic dianhydride shows a slight break in its DSC curve at 233°C.     

A Simple and Convenient Method for Syntheses of Phenolic Amino Aldehyde Ligands,enalH2 and tnalH2

New efficient methods for synthesis of enalH₂ or 1,6-bis(2-pyridyl)-2,5-bis(2-hydroxy-3-formyl-5-methylbenzyl)-2,5-diazahexane 1a and of tnalH₂ or 1,7-bis(2-pyridyl) -2,6-bis(2-hydroxy-3-formyl-5-methylbenzyl)-2,6-diazaheptane, 1b are described     

Reactive Nanocomposites as Versatile Additives for Composite Propellants

A new approach to improve the performance of composite propellants was developed in which reactive nanocomposites (RNCs) are used as replacements for aluminum powders in composite solid rocket propellants. The new materials are mechanically activated nanothermites comprising of nano‐powders of aluminum as the fuel as well as oxides of copper, iron, molybdenum, or nickel as the oxidizer. The obtained RNCs were characterized using X‐ray diffraction, scanning electron microscopy, and laser diffraction particle size analyzer. The obtained RNCs were used for preparation of modified composite solid rocket propellants (CSRPs). Burning rate, thermal decomposition behavior, heat of combustion, sensitivity, and mechanical properties of CSRPs were determined. The results showed increases in the combustion energy and the burning rate of the modified propellants were achieved, and that RNCs can be considered to be promising multi‐function additives for composite solid rocket propellants. In addition, the mechanical properties and sensitivities of the modified propellants are within the desired range.     

Thermal behavior and decomposition kinetics of composite solid propellants in the presence of amide burning rate suppressants

The employment of burning rate suppressants in the solid rocket propellant formulation is long known. Different research activities have been conducted to well understand the mechanism of suppression, but literature about the action of oxamide (OXA) and azodicarbonamide (ADA) on the thermal decomposition of composite propellant is still scarce. The focus of this study is on investigating the effect of burning rate suppressants on the thermal behavior and decomposition kinetics of composite solid propellants. Thermogravimetric analysis (TG) and differential thermal analysis have been used to identify the changes in the thermal and kinetic behaviors of coolant-based propellants. Two main decomposition stages were observed. It was found that OXA played an inhibition effect on both stages, whereas the ADA acts as a catalyst in the first stage and as coolant in the second one. The activation energy dependent on the conversion rate was estimated by two model-free integral methods: Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) based on the TG data obtained at different heating rates. The mechanism of action of coolants on the decomposition of solid propellants was confirmed by the kinetic investigation as well.     

Structural diversity in the first metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles

Metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles have been structurally characterised for the first time, complementing the significant amount of work that has been reported for the analogous pyridine ligands. N,N'-Bis(3,5-dinitrophenyl)-3,4-diphenyl-1H-pyrrole-2,5-dicarboxamide forms octahedral bis(tridentate) complexes with cobalt(iii) and nickel(ii), where the ligands are bound to the metal centres through deprotonated pyrrole and amide N atoms. N,N'-Dibutyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide and N,N'-diphenyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide also form bis(tridentate) cobalt complexes but are only deprotonated at the pyrrole N atom, the remainder of the coordination sphere comprising the thioamide S atoms. The dibutyl derivative was isolated as a Co(ii) complex, whereas the diphenyl system deposited a Co(iii) complex. In contrast, N,N'-dibutyl-3,4-dichloro-1H-pyrrole-2,5-dicarboxamide was found to act as a bidentate ligand, in an octahedral cobalt(ii) complex comprising of two bidentate pyrrole ligands, and two aqua ligands. Synthesis of N,N-bis(pyridin-2-ylmethyl)-3,4-diphenyl-1H-pyrrole-2,5-carboxamide gave a pyrrole ligand with increased denticity. Reaction with cobalt(ii) chloride resulted in the isolation of a dinuclear helicate complex. The ligand was found to have undergone addition of a methoxy group to one of the linking methylene carbons, presumably as a result of the oxidative addition of solvent methanol.     

Reexamination of the magnetic properties of Cu(2)(dca)(4)(2,5-me(2)pyz) [dca = dicyanamide; me(2)pyz = dimethylpyrazine]: isolated spin-1/2 dimers versus long-range magnetic ordering

The magnetic properties of Cu(2)(dca)(4)(2,5-me(2)pyz) have been reexamined. The extended structure of Cu(2)(dca)(4)(2,5-me(2)pyz) can be viewed in terms of Cu(2)(2,5-me(2)pyz)(4+) dimer units interconnected via mu(1,5)-dca ligands. The bulk magnetic susceptibility chi(T) and the isothermal M(H) of Cu(2)(dca)(4)(2,5-me(2)pyz) are shown to be well described by an isolated dimer model. This finding was confirmed by carrying out a spin dimer analysis based on tight-binding calculations, which shows that the 2,5-me(2)pyz ligand provides a substantial spin exchange interaction between the Cu(2+) ions while the dca ligands do not.     

两个带呋喃悬臂不对称大环双核铜配合物的合成、结构及性质(英文)

合成并表征了2个不对称大环双核铜配合物[Cu2(L1)Cl2]·CH3CN(1)和[Cu2(L2)Br2]·CH3CN·H2O(2)。配合物与CT-DNA的作用通过紫外-可见光谱,粘度实验,圆二色谱和凝胶电泳实验进行了研究。紫外-可见光谱的结果表明配合物与DNA的结合常数分别为6.2×105和7.2×105,圆二色谱的实验表明配合物能与DNA较好的结合,粘度实验表明配合物与DNA的结合为非典型的插入模式,凝胶电泳实验显示配合物通过氧化机理对DNA有较强的切割活性。     

2，5-二(2′-苯并咪唑)吡啶及其锌配合物的合成、结构与性能

本文利用微波法合成了2,5-二(2′-苯并咪唑)吡啶,采用水热合成技术得到了它的单晶(1)及其锌的配合物[Zn(C19H12N5)2(H2O)2].5H2O(2)。IR和X-射线单晶衍射实验测定和结构解析结果表明,化合物1由2,5-二(2′-苯并咪唑)吡啶和晶格水组成,化合物2中Zn2+离子与2,5-二(2′-苯并咪唑)吡啶的N原子配位,通过氢键作用形成1D链状结构,再通过配体间π-π作用形成三维结构。此外,TG和荧光测定分析表明化合物2具有良好的热稳定性和荧光性能。