三元配合物Yb[(C5H8NS2)3(C12H8N2)]的热化学性质研究

在无水乙醇中, 用吡咯烷二硫代氨基甲酸铵(APDTC)和1, 10-邻菲咯啉(o-phen·H2O)与YbCl3·3.84H2O作用, 合成了三元固态配合物, 确定它的组成为Yb[(C5H8NS2)3(C12H8N2)]. 用RD496-Ⅲ微量热计测定了298.15 K下水合氯化镱及两个配体在无水乙醇中的溶解焓, 两个配体醇溶液的混合焓及不同温度下标题化合物液相生成反应的焓变; 得到了液相生成反应的热力学参数(活化焓、活化熵和活化自由能)和动力学参数(速率常数、表观活化能、频率因子和反应级数); 通过合理的热化学循环, 求得了298.15 K时标题化合物的固相生成反应焓变; 推导了用该热量计测定固态物质比热容的计算式, 并测定了该配合物298.15 K的比热容.     

三元配合物Tm[(C5/sub>H8NS2)3(C12H8N2)]的热化学性质研究

在无水乙醇中，用吡咯烷二硫代氨基甲酸铵(APDTC)和1,10-邻菲咯啉(o-phen·H₂O)与TmCl₃·3.65H₂O作用，合成了未见文献报道的三元固态配合物，确定它的组成为Tm[(C_{5/sub>H8NS2)3(C12H8N2)]。 用RD496-Ⅲ微量热计测定了298.15 K下水合氯化铥及两个配体在无水乙醇中的溶解焓，两个配体醇溶液的混合焓及不同温度下标题化合物液相生成反应的焓变。在实验和计算基础上，得到了液相生成反应的热力学参数(活化焓、活化熵和活化自由能)，速率常数和动力学参数(表现活化能、频率因子和反应级数)。通过合理的热化学循环，求得了298.15 K时标题化合物的固相生成反应焓变；推导了用该热量计测定固态物质比热容的计算式，并测定了题目配合物298.15 K的比热容。用RBC-Ⅱ精密转动弹热量计测定了题目配合物的恒容燃烧热， 计算了它们的标准摩尔燃烧焓和标准摩尔生成焓。}     

三元配合物La[(C5H8NS2)3(C12H8N2)]生成反应的热动力学

在无水乙醇中, 用吡咯烷二硫代氨基甲酸铵(APDTC)和1,10-邻二氮菲(phen)与LaCl3·3.94H2O作用,合成了未见文献报道的三元固态配合物, 确定它的组成为La[(C5H8NS2)3(C12H8N2)]. X粉末衍射说明它为一新相化合物. IR光谱说明配合物中La3 分别与3个APDTC的6个硫原子双齿配位, 同时与phen的两个氮原子双齿配位, 配位数为8. TG-DTG分析显示其热分解为一步生成1/2La2S3 3C. 用微量热计测定了298.15 K下水合氯化镧及两个配体在无水乙醇中的溶解焓, 两个配体醇溶液的混合焓及不同温度下标题化合物液相生成反应的焓变. 在实验和计算基础上, 得到了液相生成反应的热力学参数 (活化焓、活化熵和活化自由能)和动力学参数(速率常数、表观活化能、频率因子和反应级数), 通过合理的热化学循环, 求得了标题化合物的固相反应焓变.     

固态配合物RE(C5H8NS2)3(C12H8N2)的光谱性质

在无水乙醇中, 合成了组成为RE(C5H8NS2)3(C12H8N2) (RE=La, Pr, Nd, Sm～Lu) 的固态配合物. IR光谱表明配合物中稀土离子(RE3 )与吡咯烷二硫代氨基甲酸铵 (APDC)中的硫原子和1, 10-邻菲咯琳(o-phen) 中的氮原子均双齿配位; UV光谱显示配合物中o-phen与稀土离子之间的能量传递是主要过程, 配合物的最大吸收与o-phen相比有微小的红移; FS光谱表明配合物Sm(C5H8NS2)3(C12H8N2)和Eu(C5H8NS2)3(C12H8N2)具有很强的荧光性质.     

Thermokinetics on the Reaction of Formation of the Ternary Complex Nd[（C5H8NS2）3（C12H8N2）]

Introduction The chemistry of the complexes containing lantha-nide-sulfur bond has been of substantial interest because of high performance in biological properties1 and fric-tion properties.2 In addition, they have been largely used because of their chemical and physical properties, e.g. as vulcanization accelerator.2,3 The vast investigations have been reported on preparations, characterizations and structures of these compounds,5-17 which are of great importance for illuminating the bonding…     

RE(C5H8NS2)3(C12H8N2)(RE=La,Pr,Nd,Sm)的标准摩尔生成焓测定研究

在无水乙醇中,使低水合氯化稀土(RE=La, Pr, Nd, Sm)与吡咯烷二硫代氨基甲酸铵(APDC)和1,10-邻二氮菲(σ-phen·H₂O)反应,制得其三元固态配合物.用化学分析和元素分析确定它们的组成为RE (C₅H₈NS₂)₃(C₁₂H₈N₂) (RE= La, Pr, Nd, Sm).IR光谱说明RE³⁺分别与3个PDC-的6个硫原子双齿配位,同时与σ-phen的2个氮原子双齿配位,配位数为8.用精密转动弹热量计测定了它们的恒容燃烧热Δ_cU,分别为-17776.94±7.72, -17810.41±7.93, -17762.71±7.91和-17482.42±9.35 kJ·mol^-1;并计算了它们的标准摩尔燃烧焓和标准摩尔生成焓,分别为-17792.43±7.72, -17825.90±7.93, -17778.20±7.91, -17497.91±9.35 kJ*mol^-1和-83.05±8.60, -64.70±9.40, -104.77±8.78, -388.70±10.13 kJ·mol^-1.估算出未研究的同类配合物Ce(C₅H₈NS₂)₃(C₁₂H₈N₂)和Pm(C₅H₈NS₂)₃(C₁₂H₈N₂)的和分别为-17815, -17660 kJ·mol^-1和-60, -217 kJ·mol^-1.     

Thermal decomposition of Pr[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

The thermal behavior of the complex Pr[(C5H8NS2)3(C12H8N2)] in a dry nitrogen flow was examined by TG-DTG analysis. The TG-DTG investigations indicated that Pr[(C5H8NS2)3-(C12H8N2)] was decomposed into Pr2S3 and deposited carbon in one step where Pr2S3 predominated in the final products. The results of non-isothermal kinetic calculations showed that the decomposition stage was the random nucleation and subsequent growth mechanism (n = 2/3), the corresponding apparent activation energy ?was 115.89 kJ·mol-1 and the pre-expo-nential constant ln[A/s] was 7.8697. The empirical kinetics model equation was proposed as/(α) =3/2(1-α)[-ln(1-α)]1/3.The X-ray powder diffraction patterns of the thermal decomposition products at 800℃under N2 atmosphere show that the product can be indexed to the cubic Pr2S3 phase. The transmission electron microscopy (TEM) of the final product reveals the particle appearance of a diameter within 40 nm. The experimental results show that the praseodymium sulfide nanocrystal can be prepared from thermal decomposition of Pr[(C5H8NS2)3(C12H8N2)].     

[Cu(Phen)_3][DTB]·6H_2O的合成与晶体结构

利用螯合配体1,10-邻菲咯啉(Phen)与2,2′-二硫代二苯甲酸(H2DTB)的钠盐及氢氧化铜反应合成了一种新型配合物[Cu(Phen)3][DTB].6H2O,通过元素分析、红外光谱和X射线单晶衍射等技术对其进行了表征.配合物属单斜晶系,空间群P2(1)/c,晶胞参数:a=1.822(2)nm,b=3.053(4)nm,c=2.016(3)nm,α=90°,β=106.28(4)°,γ=90°,Z=8,V=10.762(25)nm3,Dc=1.255 g/cm3,Mr=1016.57.该配合物晶体结构由配阳离子[Cu(Phen)3]2+和未配位的反荷阴离子[DTB]2-和晶格水分子组成.每个Cu(Ⅱ)原子与来自三个Phen的6个N原子配位,形成畸变的八面体结构单元.     

三元配合物Dy（Et2dtc）3（phen）的热化学性质

以铜试剂(NaEt2dtc·3H2O)和菲咯啉(phen·H2O)与低水合氯化狄(DyCl3·3.74H2O)在无水乙醇中反应,制得三元固态配合物,化学分析和元素分析确定该化合物的组成为Dy(Et2dtc)3(phen)。IR光谱表明配合物中Dy3 与3个NaEt2dtc中的6个硫原子双齿配位,同时与phen中的2个氮原子双齿配位,可推测其配位数为8。用微热量计测定出298.15 K下液相生成反应的焓变A,H曼(1)为(一19.091±0.015)kJ·mol_。,通过合理的热化学循环计算出固相生成反应焓变△rHmθ(s)为(139.641±0.482)kJ·mol-1;改变反应温度,研究了配合物的液相生成反应的热动力学,配合物的恒容燃烧能△cU用精密转动弹热量计测定为(-16730.21±9.25)kJ·mol-1,其标准燃烧焓△fHmθ和标准生成焓△fHmθ经计算分别为(-16749.42±9.25)kJ·mol-1和(-2019.68±10.19)kJ·mol～1。     

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…     

[Nd_2O(C_5H_5)_6](C_12H_9N_2)3Cl·mC_4H_8O的晶体结构

本文报告用单晶X-射线衍射法测定[Nd_2O(C-5H_5)_6](C_(12)H_9N_2)_3C1·mC_4H_5O的晶体结构。晶体属于单斜晶系,空间群为P2-1/c,晶胞参数为a=20.982(15),b=11.217(7),c=32.954(32),β=104.17(7)°;Z=4。Nd和C1原子坐标用直接法定出,其他原子坐标以差Fourier方法求得,经过最小二乘法修正,R因子为0.159。在分子中三个茂环皆通过η~5。键与Nd原子配位,两个Nd原子间存在桥氧原子,因而形成(Nd_2O(C_5H_5)_6)~(2-)阴离子,Nd-C键基本上属于离子键。三个邻菲罗啉基团通过氢键与C1原子连接形成大的阳离子[(C_(12)H_9N_2)3-C1]~(2+)。     

CRYSTAL STRUCTURE OF {Ni[(C_4H_9O)_2PS_2](C_(12)H_8N_2)_2} -[(C_4H_9O)_2PS_2]

<正> {Ni C(C4H9O)2PS2] (C12H8N2)2} [C(C4H9O)2PS2], Mr= 795. 60, Monocinic,P2,/n,a=16. 806(2), b=12. 720(2), c=21. 248(2) A. β=98. 454(7)°, V = 4493A3,Z=4,Dc= 1. 18g·cm-3,Mo Ka radiation,A=0. 71069A ,F(000) = 1664, R=0. 102 for 4154 reflections with I≥3σ(I).The crystal structure consists of complex cation {NiC(C4H9O)2PS2](C12H8N2)2}+ and complex anion C(C4H9O)2PS2]-. In the cation, nickel (Ⅱ) atom is coordinated by four nitrogen atoms and two sulfur atoms to form a distorted octahedron.     

[(C_5H_4CH_3)_2HoN_4CPh]_2·[(C_5H_4CH_3)(C_5H_5)HoN_4CPh]_2的合成和晶体结构

（C5H4CH3）3Ho和（C5H4CH3）2Ho（C5H5）与5-苯基四唑（HN4CPh）在THF中反应，得到复合产物[（C5H4CH3）2HoN4CPh]2·[（C5H4CH3）（C5H5）HoN4CPh]2，该晶体属三斜晶系，P1空间群，晶胞参数为a=9．386（3），b=13．071（3），c=16.571（2）A，a=86．90（1），β=74．61（2），γ=77.30（2）°，V=1912．2（8）A3，Z=1，Dc=1.602g／cm3，Mr=922．61，μ=41．92cm－1，F（000）=896，最终偏离因子R=0．041，Rw=0．056．晶体数据显示，在同一个晶胞里有两个组成不同的分子，每一个分子都是具有对称中心的四唑基桥二聚体结构，其桥环单元-HoN3HoN3-是平面型的。每个钬原子分别被两个茂基和3个四唑基氮原子配位，形成1个边桥变形四面体构型。     

三元配合物RE [(Pdtc)3(phen)]热化学性质的规律性

Treatment of hydrate rare-earth(RE=La,Pr,Nd,Sm-Lu)chloride with ammonium pyrrolidinyldithiocarboxy-late(apdtc)and 1,10-phenanthroline(phen)gave rise to thirteen complexes with an empirical formulaRE[(pdtc)_3(phen)].The enthalpies of solution of hydrate rare-earth(RE= Sm-Ho,Tm-Lu)chloride,apdtc and phenin ethanol were measured by an RD-496 Ⅲ microcalorimeter at 298.15 K,along with the mixing enthalpy of etha-nol solution of APDC and that of phen and the enthalpies of reaction of formation of the title complexes in ethanol.The enthalpies of reaction of formation of the title complexes in solid were available through a rationally thermo-chemical cycle.Using an RD-496 Ⅲ microcalorimeter,a model was developed for calculating the specific heat ca-pacity and the responding specific heat capacity of the complexes were determined.The thermochemical properties,including the enthalpies of solution of hydrate rare earth chloride in ethanol,the enthalpies of reaction of formationof the title complexes in ethanol,the enthalpies of reaction of formation of the title complexes in solid,the specialheat capacities at room temperature,the standard molar enthalpies of combustion and the standard molar enthalpiesof formation for this series of complexes versus the atomic numbers of rare earth,presented triplet effect,which isrepresentative of certain covalent bond between RE and the ligands and the result of 4f electron not shielded fullyby 5s5p.     

Ce(C_8H_8)_2和Ce(C_8H_8)_2~-的化学键性质

结合改进的重叠模型Xa-SW法和Ziegler过渡态法,通过将中心原子与配体的作用选成离子聚集、中心原子只有s和p轨道参与成键、中心原子只有d轨道参与成键、中心原子只有f轨道参与成键、中心原子的s、p、d和f轨道同时参与成键5种类型,从能量角度分析了Ce(C_8H_8)_2和Ce(C_8H_8)~-_2的化学键性质。     

Molecular Structure of Organolanthanide Complex ［（η~5－CH_3C_5H_4）_2Tb（μ－Cl）（THF）］_2

ＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆＯｒｇａｎｏｌａｎｔｈａｎｉｄｅＣｏｍｐｌｅｘ［（η~５－ＣＨ_３Ｃ_５Ｈ_４）_２Ｔｂ（μ－Ｃｌ）（ＴＨＦ）］_２ＷＵＺｈｏｎｇ－Ｚｈｉ；ＨＵＡＮＧＺｕ－Ｅｎ；ＣＡＩＲｕｉ－Ｆａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅ...     

Keggin型配合物（C12H9N2）3[PMo12O40]的水热合成及晶体结构

采用水热反应合成了有机-无机杂化的Keggin型配合物（C12H9N2）3[PMo12O40],并通过X-射线单晶衍射对其结构进行了分析。该配合物为正交晶系P212121空间群,晶胞参数为a=1.20800（1）nm,b=2.10108（4）nm,c=2.24234（5）nm。配合物包含了孤立的Keggin型[PMo1...