配合物Ni（HDPC）2·3H2O和Cu（DPC）（H2DPC）·2H2O的制备及反应热动力学

吡啶-2,6-二甲酸（Pyridine-2,6-dicarboxylic acid,H2DPC）是一个灵活多变的刚性配体,能提供N原子和O原子与过渡、非过渡和稀土金属离子鳌合形成稳定的配合物,与过渡金属离子形成的配合物在催化、磁性、发光和医药等方面具有潜在的应用价值。H2DPC与Ni^2＋和Cu^2＋形成的配合物的晶体结构已有文献报道,但有关该类配合反应热动力学研究来见文献报道。本文用微量热法分别对NiCl2和CuCl2与H2DPC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。     

[Zn2（C7H8O6）2（bipy）2（H2O）2]·4H2O手性配位聚合物的合成与晶体结构

采用溶剂热技术合成了一种新型手性配位聚合物[Zn2（C7H8O6）2（bipy）2（H2O）2]·4H2O（C7H8O6=2,3-氧-异丙叉基-L-酒石酸根,bipy=4,4′-联吡啶）,并通过单晶X射线衍射结构分析、元素分析、热重分析以及红外光谱进行了表征.结构分析数据表明,该化合物属单斜晶系,C2空间群,晶胞参数a=2.02334（14）nm,b=1.13896（4）nm,c=1.01094（6）nm,β=117.366（3）°,V=2.0689（2）nm^3.两个晶体学独立的Zn原子均为八面体构型,其中Zn1原子赤道配位点被2个酒石酸根中的4个羧酸根氧螯合配位,2个酒石酸根中剩下的4个羧酸根氧中的2个分别与2个Zn2原子连接形成无限一维链,Zn2原子的另外2个反式赤道配位点被2个水分子氧占据,同时这两种Zn原子的轴向配位点均被4,4′-联吡啶的氮原子占据,形成具有矩形格子[0.51165（3）nm×1.13896（5）nm]的二维层状结构,游离的2个水分子通过氢键作用形成二聚体,并与酒石酸根中未与Zn配位的羧酸氧连接,把二维层状结构连接成三维网状的超分子结构.     

Low-Temperature Heat Capacities and Thermodynamic Properties of Hydrated Nickel L-Threonate Ni（C4H7O5）2·2H2O（S）

Low-temperature heat capacities of the compound Ni（C4H7O5）2·2H2O（S） have been measured with an auto- mated adiabatic calorimeter. A thermal decomposition or dehydration occurred in 350--369 K. The temperature, the enthalpy and entropy of the dehydration were determined to be （368.141 ±0.095） K, （18.809±0.088） kJ·mol ^-1 and （51.093±0.239） J·K^-1·mol^-1 respertively. The experimental values of the molar heat capacities in the temperature regions of 78-350 and 368-390 K were fitted to two polynomial equations of heat capacities （Cp,m） with the reduced temperatures （X）, [X=f（T）], by a least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated on the basis of the fitted polynomials. The smoothed values of the molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated with an interval of 5 K.     

Rapid Thermolysis Studies of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O）

T-jump/FT-IR spectroscopy was used to study the rapid thermal decomposition activity of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O） under 0.1 MPa Ar atmosphere. The results show that the main gaseous products of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O are NH3, H2O and HONO, while CO and NO are the major gaseous products of flash pyrolysis of Cd（CHZ）2（TNR）（H2O）. Thus Cd（CHZ）2（TNR）（H2O） is not an eco-friendly and chemically compatible primary explosive. Both compounds liberate volatile metal carbonate, oxide and isocyanate compounds. The combustion temperature and products of the two compounds were calculated by Real code. The results of theoretical calculation show that the combustion temperature of [Pb2（TNR）2（CHZ）2（H2O）2].4H2O is higher than that of Cd（CHZ）2（TNR）（H2O）, there is no HNCO in the combus- tion products and the amount of NO is less than the experiment result from T-jump/FTIR.     

Ni（bpy）（H2O）（V2O6）和[Ni（bpy）2]2（V6O17）的水热合成与晶体结构

用NiCl2·6H2O,2,2＇-联吡啶（bpy）,NH4VO3,WO3在443K下通过水热反应法得到了两种多钒酸镍配合物Ni（bpy）（H2O）（V2O6）（1）和[Ni（bpy）2]2（V6O17）（2）．单晶X射线衍射结果表明化合物（1）属于正交晶系,空间群为Pcα2（1）,晶胞参数为0=0．91704（18）nm,b=1．0519（2）nm,c=1．4336（3）nm,V=1．3830（5）nm^3,Z=4;化合物（2）属于单斜晶系,空间群为P2（1）／c,晶胞参数为α=1．5467（3）nm,b=1．4740（3）nm,c=1．0457（2）nm,β=91．99（3）°,V=2．3826（8）nm^3,Z=4．化合物（1）由2,2’-联吡啶修饰的二维[Ni（V2O6）（H2O）]∞电中性层构成,而化合物（2）则由2,2＇-联吡啶修饰的、呈正弦波浪状的[Ni：（V6O17）]∞二维电中性层构成．     

[（C6n5NO2）Pr（H2O）4]（CrMo6O24H6）·（C6H5NO2）·2．5H2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[（C6n5NO2）Pr（H2O）4]（CrMo6O24H6）·（C6H5NO2）·2．5H2O,通过红外光谱和X射线单晶衍射对其进行了表征．结果表明,该化合物属于单斜晶系,C2/c空间群．a=2．3442（9）nm,b=1．3291（5）nm,c=2．458（1）nm,β=103．08（1）°,V=7．460（5）nm^3,R1=0．0727,wR2=0．1903．结构分析表明,[CrMo6O24H6]^3-阴离子通过端氧担载一个配位的Pr^3＋离子形成中性的（C6H5NO2）Pr（H2O）4（CrMo6O24H6）基团,相邻的中性基团在O1-Pr-O1桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构．     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

镍配合物[Ni（phen）：（tovsb）]·4H2O的合成与晶体结构

以牛磺酸、邻香草醛为原料,合成了配体牛磺酸缩邻香草醛席夫碱,再用所得配体与醋酸镍、邻菲啰啉作用,合成了配合物[Ni（phen）2（tovsb）]·4H2O（phen=邻菲啰啉,tovsb=牛磺酸缩邻香草醛席夫碱）,其结构通过IR,元素分析和x-射线单晶衍射法测定。标题配合物属三斜晶系,PI空间群;α=1．04661（16）,b=1．2303（2）,c=1．4063（2）nm,α=83．714（4）,β=88．539（3）,γ=69．398（3）°,V=1．6947（5）nm^3,Z=2。结构分析表明,两个邻菲哕啉共提供四个配位原子,牛磺酸缩邻香草醛席夫碱提供两个配位原子,中心Ni（Ⅱ）离子是一个六配位的畸变八面体结构。该聚合物中含有四个结晶水分子,水分子通过氢键作用,形成了一个六聚水簇。配合物分子通过氢键和π-π堆积作用形成三维超分子结构。     

[（phen）2Mn2（μ—O）（μ—Ac）2（H2O2）]（ClO4）2·4H2O双核锰？…

MnAc3.2H2O在pH=4.0的HAc-NaAc缓冲溶液中和邻菲罗啉(phen)反应, 制得了双核锰(Ⅲ)合物[(phen)2Mn2(μ-O)(μ-Ac)2 (H2O)2](ClO4)2.H2O, 并进行了红外光谱表征. X射线单晶衍射表明, 该晶体属单斜晶系, 空间群P21/n, 晶胞参数: a=1.025 28(5) nm, b=1.792 75(9) nm, c=1.984 14(10) nm, β=94.843 0(10)°, V=3.634 0(3) nm3, Z=4, Dc=1.669 g.cm-3. 紫外可见光谱在480 nm处有一个吸收峰. 循环伏安实验说明, 此配合物在乙腈溶液中经历了一个半可逆的一电子氧化还原过程.     

配合物[Mn2（α-Furacrylic radical）4（phen）2（H2O）]·H2O的合成、晶体结构及热稳定性

羧酸因其具有多样的配位方式、能减缓抗衡离子效应的负电性以及羧基氧原子易参与形成氢键而被广泛应用于配合物的合成中。α-呋喃丙烯酸是一种应用广泛的羧酸．有抑菌活性．作为有机合成中间体,可用来制备庚酮二酸、庚二酸,是制备塑料、合成树脂的重要原料;在医药工业上用于合成防治血吸虫病药-呋喃丙胺;     

Synthesis and Structure of [Er4（μ3—OH）4（Hpro）4（Pro）2（H2O）7]（ClO4）6.7H2O

1 INTRODUCTION The design and synthesis of polynuclear com- plexes have attracted chemists?attention in the contemporary chemistry, since their clusters maybe lead to novel materials with magnetic, optical, electronic and catalytic properties of the constituent metals[1～3]. It is also prevalently interesting to synthesize high-nuclearity metal complexes for their nanoscopic dimensions[3, 4]. Spectroscopic properties of the lanthanides are widely used in the study of biological systems. …     

配合物[Sm（C7H5O3）2（C4H6NO2S）]·2H2O的热化学研究

将六水氯化钐,水杨酸与硫代脯氨酸3种物质一起反应,制得了一种新的稀土三元固体配合物[Sm（C7H5O3）2（C4H6NO2S）].2H2O（s）。通过红外光谱、热重差热分析、元素分析等手段确定了其结构与组成。在常压、298.15 K下,分别测定了六水氯化钐、水杨酸、硫代脯氨酸和该配合物在混合溶剂（二甲亚砜∶乙醇∶3 mol.L-1HCl=1∶1∶1）中的溶解焓,并根据热化学原理得出了298.15 K时配合物[Sm（C7H5O3）2（C4H6NO2S）].2H2O（s）的标准摩尔生成焓ΔfHmΘ=（-2913.73±3.10）kJ.mol^-1。     

A New Heteropolyoxotungstate with a Three-dimensional All-inorganic Framework [（C2H4N2）4（P4Co3W4O（28）H6）（H2C2O4）]n

A new heteropolyoxotungstate [(C2H4N2)4(P4Co3W4O28H6)(H2C2O4)]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006(17),b = 17.1006(7),c = 10.7525(5),V = 3144.2(2)3,Z = 4,Dc = 3.795 g·cm-3,F(000) = 3300,MoKα(λ = 0.71073 ),μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.     

由己二酸根桥联的新颖双U形四核铜配合物：[Cu4（phen）4（NO3）2（H2O）2（adip）4／4（Hadip）4／2]（NO3）2·2H2O

邻菲罗啉、己二酸和硝酸铜在水溶液中反应得到一种新颖的四核铜配合物[Cu4（phen）4（NO3）2（H2O）2（adip）4／4（Hadip）4／2]（NO3）2·2H2O（其中H2adip=己二酸）,并经元素分析,IR,UV,TG和X射线单晶衍射分析表征．该配合物晶体属三斜晶系,P1空间群,a=1．0146（2）nm,b=1．0261（2）nm,c=1．8285（4）nm,α=91．66（3）°,α=92．19（3）°,γ=112．76（3）°,V=1．7520（6）nm3,Z=1,Dc=1．639g／cm3,C66H66Cu4N12O28,Mr=1729．47,F（000）=886,μ=1．294mm^-1,R1和wR2分别为0．0447和0．1141．己二酸根通过4个羧基O将两个U形双核亚单元联接成具有一个对称中心的双U形四核结构,其中每个U型亚单元包含晶体学上不对称的2个Cu（Ⅱ）原子．每个Cu（Ⅱ）离子均处于畸变的四方锥配位环境,除与己二酸氢根（Hadip）、己二酸根（adip）和邻菲罗啉（Phen）的N,O配位形成锥底平面外,其中的1个Cu（Ⅱ）与水配位,而另一个Cu（Ⅱ）则与硝酸根配位．配合物晶体结构中存在着广泛的氢键和π…π作用．