Eu_2(p-ClC_6H_4COO)_6(C_(12)H_8N_2)_2配合物热分解机理及非等温动力学

0 IntroductionThe complexes formed by rare earth and aromatic carboxylic acid have many special structuresand interesting luminous properties, thus arouse people's interest to study them. They can be used.in many areas such as extraction and separation, germicide, catalyst, luminous materials andfunctional materials and so on.The crystal structure and luminescence spectra of the europium p-chlorobenzoate complex withl, 10-phenanthroline has been reported"], but the study for its non-isothermal…     

配合物[Tb(p-ClBA)3(phen)]2的结构和性能

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb(p-ClBA)₃(phen)]₂(1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(III) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(III) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)₃(phen)]₂ is quite stable to heat. CCDC: 221921.     

［Eu2(o-ClC6H4OCH2COO)6(C12H8N2)2(H2O)2］·(CH3)2SO的晶体结构和荧光光谱

标题配合物M=1892.01,单斜晶系,空间群P2₁/c, a=1.2975(3) nm, b=2.6591(9) nm, c=1.2118(3) nm, β=96.95(1)°, Z=2, D_c=1.577 g/cm³, T=293(2)K。最终的偏离因子R=0.0583。该配合物以二聚体形式存在,通过其中的桥联羧基形成了双核分子。该分子中羧基具有桥联双齿、桥联三齿和单齿三种配位模式,Eu-Eu之间的距离为0.4019(1) nm。在77K下测得配合物中Eu(Ⅲ)离子仅有一种格位。 ⁵D₀→ ⁷F_J(J=0～2)跃迁光谱说明Eu(Ⅲ)离子格位具有C₂对称性。     

烟酰胺铬(Ⅲ)配合物的合成及其热分解脱水非等温动力学研究

本文合成了铬（Ⅲ）的一个新的双核配合物Ｃｒ２（Ｎｉｃａ）４Ｃｌ５（ＯＨ）（Ｈ２Ｏ）６（Ｎｉｃａ表示烟酰胺．通过元素分析、摩尔电导、红外光谱、热重．对该配合物进行了表征，表明烟酰胺以吡啶氮与铬（Ⅲ）配位．文章对该配合物进行了热分解脱水非等温动力学研究，运用Ａｃｈａｒ法与Ｃｏａｔｓ—Ｒｅｄｆｅｒｎ法，推断出该热分解脱水反应为二级反应．其动力学方程为ｄα／ｄｔ＝Ａｃ（－Ｅ／ＲＴ）（１－α）２，动力学补偿效应表达式为ＩｎＡ＝０．２９９２Ｅ－１０．５６８２．     

超分子化合物 [Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O 的热分解非等温动力学

用非等温热重法研究了Eu(III)的化合物[Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H2O)₃]₂·phen·4H₂O 的热分解及其动力学，并用Kissinger和Ozawa 方法计算了第一分解阶段的活化能.     

[Mn(NH2NHCO2C2H5)3](NO3)2的晶体结构和热分解机理

[Mn(ECZ)₃](NO₃)₂ is newly prepared by the aqueous solutions of Mn(NO₃)₂ and ethyl carbazate (ECZ). The crystal structure has been determined by X-ray crystal diffraction analysis. It belongs to monoclinic with space group of P2₁/n. The crystal parameters are: a=1.3974(2) nm, b=0.8796(2) nm, c=3.4322(7) nm, β=91.25(1) °, V= 4.2175(1) nm³, Z=8. Its molecular weight is 491.30. Mn²⁺ is located on the center of the molecular structure. Ethyl carbazate serves as a bidentate ligand which coordinates to the metal cations with its carbonyl oxygen atom and the terminal hydrazine nitrogen atom, forming five-member chelating rings, and three such rings are formed in each molecule. The coordination number of the metal ion is six and the coordination configuration of the central ion is octahedral. Specially, antimer configuration phenomenon is found in the molecule. The complex is further characterized by element analysis and IR measurements. The thermal decomposition mechanism is studied by using TG-DTG and DSC techniques. CCDC: 215675.     

双核Cu(Ⅰ)配合物的热分解非等温动力学

由于钢作为活性配位中心离子，存在干具有生物功能的蛋白质大分子中，近年来钢的配位化学受到广泛关注．普遍认为，咪唤基在铜蛋白的配位化学中起重要作用＊，开展钢与具咪陵基配体所形成配合物的研究，有助于揭示钢在蛋白质中的生物化学功能及其与咪哩基等其它基团相互键合作用的本质．我们曾报导了四种新型具苯并咪吐基双核CIJ（）配合物：［CllZ’（OCTB）flC104h·1．SHZO川，［Cll。’（NMOCTB）］·（CIO。）。·H。O（2），［Cll。’（NBUOCTB）］（CIO。）z切，［Cll。’（NBOCTB）］·（CIO4h·H。O（4）的合…     

双核Cu(I)配合物的热分解非等温动力学

Thermal decomposition process of four benzimidazolyl-containing dicopper(Ⅰ) complexes: [Cu2(OCTB)](ClO4)2•1.5H2O(1), [Cu2 (NMOCTB)](ClO4)2•H2O(2), [Cu2(NBUOCTB)](ClO4)2(3), [Cu2(NBOCTB)](ClO4)2•H2O(4) and their kinetics were studied under the non-isothermal conditions by TG-DTG techniques. The non-isothermal kinetic data were analyzed by means of Achar and Coats-Redfern method respectively. The kinetic equation for the second step of the decomposition of complex (1) can be expressed as: dα/dt=A•exp(-E/RT) •(1-α), the mechanism of this reaction corresponds to "Coring and Growth" with n=1; while for the first step of complex (3) decomposition, dα/dt=A•exp(-E/RT)• (1-α)2, which corresponds to the mechanism of "the second-order chemical reaction".     

混合配体的铜(Ⅱ)配合［Cu(C2H4O2N)(C12H8N2)(H2O)］.ClO4.2.5H2O的合成、性质及晶体结构

本文对甘氨酸、1,10-邻菲咯啉铜(Ⅱ)固体配合物进行了合成和表征,并利用X射线分析研究了其晶体结构。     

Studies on Non-isothermal Kinetics of the Thermal Decomposition of Eu2(BA)6(bipy)2

The thermal decomposition of Eu₂(BA)₆(bipy)₂ (BA=C₂H₅N^– ₂, benzoate; bipy=C₁₀H₈N₂, 2,2'-bipyridine)and its kinetics were studied under the non-isothermal condition by TG-DTG, IR and SEM methods. The kinetic parameters were obtained from analysis of the TG-DTG curves by the Achar method, the Madhusudanan-Krishnan-Ninan (MKN) method, the Ozawa method and the Kissinger method. The most probable mechanism function was suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as: dα/dt=Aexp(–E/RT)3(1–α)^2/3. This revised version was published online in August 2006 with corrections to the Cover Date.     

双核铕-苯甲酸-邻菲咯啉三元络合物非等温热分解动力学研究

采用TG-DTG和DTA技术研究了Eu2(BA)6(PHEN)2 (BA苯甲酸根离子;PHEN1,10-邻菲咯啉)在静态空气中的热分解过程,根据TG曲线确定了热分解过程中的中间产物及最终产物,运用Acher法、Madhusudanan-Krishnan-Ninan (MKN)法和Flynn-Wall-Ozawa法对非等温动力学数据进行分析,推断出第一步热分解反应的动力学方程为dα/dt=Aexp(-E/RT)(1-α)2, 第一步热分解反应的活化能为135 kJ/mol, 活化自由能ΔG为149 kJ/mol, 活化焓ΔH为129 kJ/mol, 活化熵ΔS为-33 J/(mol·k), 同时用等温TG法得到失重10%为寿终指标的寿命方程为lnτ=-22.66+1.646×104/T.     

钐-邻硝基苯甲酸与1，10-邻菲咯啉配合物的热分解动力学

The complex of Sm₂(o-NBA)₆(PHEN)₂ (o-NBA, o-Nitrobenzoate; PHEN, 1,10-phenanthroline) was prepar-ed and characterized by elemental analysis, IR and UV spectraoscopy. The thermal decomposition mechanism of Sm₂(o-NBA)₆(PHEN)₂ was studied under a static air atmosphere by TG-DTG. The thermal decomposition kinetics of the complex for the first stage was studied under non-isothermal condition. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: G(α)=[-ln(1-α)]^1/2, f(α)=2(1-α)[-ln(1-α)]^1/2. The activation energy E for the first stage is 259.50 kJ·mol^-1, the pre-exponential factor A is 36.19×10¹⁸ min^-1. The lifetime equation at weight-loss of 10% was deduced as lnτ=-36.70+27 572.12/T by isothermal thermogravimetric analysis.     

Cu[C5H3N(CCH3=N-C6H5)2]2(PF6)2配合物的合成、晶体结构和热分解反应动力学

The title complex Cu[C₅H₃N(CCH₃=N-C₆H₅)₂]₂(PF₆)₂ has been synthesized by reaction of Schiff base C₅H₃N(CCH₃=N-C₆H₅)₂ and cupric sulfate in toluene solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 1041.85. The crystal structure belongs to triclinic system with space group P1 and cell parameters: a=12.6470(10)?, b=14.123(2)?, c=15.613(2)?;α=66.150(10)°,β=79.470(10)°,γ=78.290(10)°, V=2481.6(5)?³, Z=2, D_c=1.394Mg·m^-3 and F(000)=1064. The final R[I >2σ(I)]:R₁=0.0668, wR₂=0.1927; R(all data): R₁=0.1133, wR₂=0.2357. The Cu(Ⅱ) was coordinated by six nitrogen, at the same time the Cu(Ⅱ) formed a distorted octahedron, besides the angles and planes of this compound were discussed . The result of kinetics of the thermal decomposition indicated that the first step of it is 2 series chemical reactions, the function of machanism is f(a)=(1-a)², and the activation energy is 144.64E/kJ. CCDC: 180872.     

稀土配合物[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3的标准生成焓及热分解动力学研究

合成了高氯酸镨和咪唑(C₃H₄N₂), DL-α-丙氨酸(C₃H₇NO₂)混配配合物晶体. 经傅立叶变换红外光谱、化学分析和元素分析确定其组成为[Pr(C₃H₇NO₂)₂(C₃H₄N₂)(H₂O)](ClO₄)₃. 使用具有恒温环境的溶解-反应量热计, 以2.0 mol•L^－1 HCl为量热溶剂, 在T＝(298.150±0.001) K时测定出化学反应PrCl₃•6H₂O(s)＋2C₃H₇NO₂(s)＋C₃H₄N₂(s)＋3NaClO₄(s)＝[Pr(C₃H₇NO₂)₂(C₃H₄N₂)(H₂O)](ClO₄)₃(s)＋3NaCl(s)＋5H₂O(1)的标准摩尔反应焓为Δ_rH_m^ө＝(39.26±0.11) kJ•mol^－1. 根据盖斯定律, 计算出配合物的标准摩尔生成焓为Δ_fH_m^ө{[Pr(C₃H₇NO₂)₂(C₃H₄N₂)(H₂O)](ClO₄)₃(s), 298.150 K}＝(－2424.2±3.3) kJ•mol^－1. 采用TG-DTG技术研究了配合物在流动高纯氮气(99.99%)气氛中的非等温热分解动力学, 运用微分法(Achar-Brindley-sharp和Kissinger法)和积分法(Satava-Sestak和Coats-Redfern法)对非等温动力学数据进行分析, 求得分解反应的表观活化能E＝108.9 kJ•mol^－1, 动力学方程式为dα/dt＝2(5.90×10⁸/3)(1－α)[－ln(1－α)]^－1exp(－108.9×10³/RT).     

邻甲基苯甲酸铕与邻啡咯啉络合物的热分解动力学及寿命

采用TG DTG技术研究了Eu2 (o MBA) 6 (PHEN) 2 (o MBA :邻甲基苯甲酸根离子 ;PHEN :1 ,1 0 邻啡咯啉 )在静态空气中的非等温热分解机理及动力学。根据TG曲线确定了热分解过程中的中间产物及最终产物。运用Acher法、Madhusudanan Krishnan Ninan (MKN)法和Ozawa法对非等温动力学数据进行分析 ,得到第一步热分解反应的机理函数和动力学参数 ,同时用等温TG法得到失重 1 0 %为寿终指标的寿命方程 :lnτ=-2 4 3 690 +1 .5 2 84× 1 0 4 T。     

Crystal structure of [Mn(1,10-C12H8N2)3](B6H7)2

A new compound [MN^II(Phen)₃]²⁺(B₆H₇)₂⁻ is synthesized; its crystal structure is studied by XRD at 100 K. Crystallographic data: C₃₆H₃₈B₁₂N₆Mn, M = 739.39, triclinic symmetry, space group P , unit cell parameters: a = 10.3131(3) ?, b = 13.4839(4) ?, c = 15.1132(4) ?; α = 97.696(1)°, β = 108.324(1)°, γ = 102.211(1)°; V = 1903.9(1) ?³, Z = 2, d _calc = 1.290 g/cm³. The structure is solved by direct and Fourier methods and refined by full-matrix LSM in the anisotropic (isotropic for hydrogen atoms) approximation to the final factor R ₁ = 0.036 for 10169 I _hkl ≥ 2σ _I (Bruker-Nonius X8 APEX CCD diffractometer, λMoK _α). The structure contains two crystallographically different anions. Original Russian Text Copyright ? 2009 by T. M. Polyanskaya, M. K. Drozdova, V. V. Volkov, and K. G. Myakishev __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 381–385, March–April, 2009.     

配合物Cu(C15H12N2O3)(C5H5N)的合成和晶体结构

The title coordination compound with N-substituted-salicyl Schiff ligand, Cu(C₁₅H₁₂N₂O₃)(C₅H₅N), has been synthesized. The coordination compound crystallizes in orthorhombic system, space group Pbca with a=2.037 62(7) nm, b=0.698 45(2)nm, c=2.508 76(9)nm, V=3.570 4(2) nm³, Z=8, F(000)=1 688, D_c=1.529 g·cm^-3, M_r=410.91, μ=1.250 mm^-1, R=0.031 3 and wR=0.077 0. In the coordination compound, one phenolate oxygen, one carbonyl oxygen and one hydrazine nitrogen atom from the dianionic ligand N-salicylaldehyde-N′-(4-methoxybenzoyl) hydrazone and one pyridine nitrogen atom coordinate to Cu(Ⅱ) ion, forming a distorted square plane. CCDC: 218182.