三元配合物Tm[(C_5H_8NS_2)_3(C_(12)H_8N_2)]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[(C5H8NS2)3(C12H8N2)]。用RD496-Ⅲ微量热计测定了298.15K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298.15K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298.15K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。     

组氨酸锌配合物生成反应的热动力学研究

用微量量热法对醋酸锌与组氨酸在水中的反应进行了热动力学研究。通过实验和计算得出了该反应的热动力学参数 (活化焓、活化熵、活化自由能 )、速率常数和三种动力学参数 (活化能、指前因子及反应级数 )。并对温度改变对该反应的影响及配合物的合成条件进行了讨论。     

铈和硫代脯氨酸、水杨酸三元配合物的热化学性质

用七水合氯化铈与硫代脯氨酸(C4H7NO2S)和水杨酸(C7H6O3)合成了三元固体配合物[Ce(C7H5O3)2(C4H6NO2S)]·2H2O。根据盖斯定律设计一个热化学循环,用恒温环境的溶解―反应量热法研究得到合成反应的标准反应焓为263.12±0.95 kJ/mol,进而算出配合物298.15 K时的标准摩尔生成焓为-2785.7±3.2 kJ/mol。     

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.     

稀土硝酸盐与组氨酸配合物的研究

用半微量相平衡法研究了RE(NO3)3-His-H2O(RE=Sm,Gd,Er)在25℃及全浓度范围内的溶度性质. 结果表明每个体系中分别形成两种不同摩尔比的配合物:RE(His)(NO3)3.H2O和RE(His)3(NO3)3.2H2O,它们均属固液一致溶解化合物. 在相平衡结果指导下,合成了文献中未见报道的配合物RE(His)(NO3)3.H2O(RE=La～Nd,Sm～Lu,Y),用化学分析和元素分析确定了它们的组成,并通过光谱、热谱研究了它们的性质,用转动弹热量计测定了他们的燃烧能,计算出它们的标准生成焓.     

三烟酰胺铬(Ⅲ)配合物的合成及其热分解非等温动力学研究

合成了铬 ( )的一个新配合物 Cr(Nica) 3 (H2 O) 3 (NO3 ) 3 ·H2 O(Nica表示烟酰胺 ) ,并对其进行了热分解非等温动力学研究。通过摩尔电导、紫外可见光谱、红外光谱、X-射线粉末衍射等 ,对其结构进行了表征。运用 Achar法与 Coats- Redfern法 ,对非等温动力学数据进行分析 ,推断第二步热分解反应按动力学方程 dα/ dt=Ae-ERT· 32 (1 α) 23 [(1 α) 1 3 - 1 ] -1进行 ,同时给出了热力学补偿效应表达式。     

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。     

新型三元配合物[RE(C_7H_5O_3)_2(C_6H_4NO_2)·H_2O](RE=La,Ce,Nd)的合成、光谱特性和热化学性质

采用均匀沉淀法,在20%的乙醇水溶液中,用水杨酸、维生素B3与稀土硝酸盐合成了一类新的稀土三元配合物.通过元素分析、化学分析、摩尔电导、红外光谱、紫外光谱、热重-微分热重分析等手段对配合物的结构和性质进行表征,确定了它们的组成通式为[RE(C7H5O3)2(C6H4NO2)·H2O](RE=La,Ce,Nd).维生素B3吡啶环上的N原子和水杨酸的酚羟基均未参与配位,两种配体均是脱质子后以羧酸根与RE3+离子配位,且成键以离子性为主,兼有部分共价性.在298.15 K,用精密的溶解-反应热量计分别测量了配位反应相关各物质的溶解焓,根据盖斯(Hess)定律求得合成反应的标准摩尔反应焓r mHФ分别为:(180.61±0.72)、(187.25±0.68)和(185.61±0.26)kJ/mol.进而求出配合物的标准摩尔生成焓为:f mHФ[La(C7H5O3)2(C6H4NO2)·H2O(s),298.15 K]=-(2493.9±2.9)、f mHФ[Ce(C7H5O3)2(C6H4NO2)·H2O(s),298.15 K]=-(2441.0±2.8)和f mHФ[Nd(C7H5O3)2(C6H4NO2)·H2O(s),298.15 K]=-(2463.1±2.9)kJ/mol.     

硫酸锌与组氨酸固液反应的热动力学研究

用微热量计对硫酸锌与组氨酸在水中的固液反应进行了热动力学研究。通过实验和计算得出了该反应的热动力学参数（活化焓,活化熵及活化自由能）,速率常数和动力学参数（活化能,指前因子及反应级数）,并对温度改变对该反应的影响及配合物的合成条件进行了讨论。     

用微量热法研究亚甲基蓝与溴酸根的氧化还原反应的热动力学

用微热量计对亚甲基蓝与溴酸根在水中的氧化还原反应进行了热动力学研究.根据在微量热计上测得的数据和算得该反应的热力学参数(活化焓、活化熵及活化自由能)、数率常数和动力学参数(活化能、指前因子及反应级数),对此反应的机理也作了探讨.     

Kinetics and Mechanism of the Thermal Decomposition of M(NO3)2·nH2O (M=Cu,Co, Ni)

This paper presents the results of simultaneous DTA-TG-DTG and DSC studies on the thermal decomposition of Cu(NO3)2·3H2O, Co(NO3)2·6H2O and Ni(NO3)2·6H2O in an air atmosphere. The mechanism and enthalpies of the investigated processes were determined, as well as the kinetic parameters of the processes run under non-isothermal conditions by means of Kissinger's method. The dependence of the activation energy on the ionic radius of the cations building up the crystal lattices of the investigated compounds was also studied. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermokinetic Study on the Complexation Reaction of the First-Row Transitional Metal Chlorides with Histidine

Introduction The first-row transitional metals of chromium, man-ganese, iron, cobalt, nickel and copper are essential trace elements to human body, which are connected with hundreds of metalloproteins and metalloenzymes, participating in ferment syntheses and playing an im-portant role in metabolism of nucleic acid, protein, carbohydrate and fat. L--histidine is one of the basic units of proteins and absorbed from food because of not being synthesized in human body. Therefore, it is of practic…     

六亚甲基四胺锑(Ⅲ)、铋(Ⅲ)配合物的固相合成与表征

通过固相反应,合成了新的配合物六亚甲基四胺锑(Ⅲ)、铋(Ⅲ):SbCl3(C6H12N4)2·H2O(1)、BiCl3(C6H12N4)2·H2O(2).经元素分析、X 射线粉末衍射、远红外光谱和差热 热重分析进行表征,确定了配合物的组成和结构.对XRD谱指标化,确定其晶系和晶胞参数.SbCl3(C6H12N4)2·H2O(1):a=1.2490nm,b=1.4583nm,c=1.6870nm,β=91.78°,V=3.0706nm3;BiCl3(C6H12N4)2·H2O(2):a=1.3250nm,b=1.3889nm,c=1.7449nm,β=98.94°,V=3.1725nm3.     

YbCl3·3H2O-18-C-6-CH3COCH3体系(25℃)的相化学研究与 固态配合物的合成与 性质

采用半微量相平衡方法研究了YbCl3·3H2O-18-C-6-CH3COCH3三元体系(25℃)的溶度,测定了各饱和溶液的折光率,绘制了体系的溶度图与饱和溶液折光率曲线,考察了相平衡过程中水的行为。体系中形成两种化学计量的新配合物：2YbCl3·18-C-6·6H2O·CH3COCH3(1)与YbCl3·18-C-6·3H2O·0.5CH3COCH3(2),两者均为固液异成分溶解的配合物。比较讨论了盐的阴离子与溶剂对形成配合物的影响。在相平衡结果指导下,制备了固态配合物,用化学分析、元素分析、IR,DTG,TG与DSC研究了固态配合物的组成与性质,预示了固态配合物YbCl3·18-C-6·3H2O与YbCl3·18-C-6的配位结构。     

Reactions of 2-(1-carboxyl-2-hydroxyphenyl)thiazolidine with chromium(III) salts leading to newer synthesis of chromium(III) complexes

Reactions of 2-(L-carboxyl-2-hydroxyphenyl)thiazolidine with different chromium(III) salts [CrCl₃?·?6H₂O, K₃[Cr(SCN)₆], NH₄[Cr(NH₃)₂(SCN)₄]?·?H₂O, [Cr(urea)₆]Cl₃?·?3H₂O and [Cr(CH₃COO)₂H₂O]₂] under varied reaction conditions afforded many new mixed-ligand chromium(III) complexes. The ligand is a tridentate dibasic NSO donor except for complexes 1 and 4 where two moles of the ligand are present for each molecule of complex, one functioning as a dibasic tridentate (NSO) and the other as a monobasic bidentate (NS) (phenolic OH and carboxylic COOH groups remaining uncoordinated). The complexes have been characterized by elemental analyses, magnetic susceptibilities, molar conductances, molecular weights and spectroscopic (IR, Uv-vis) data. The ligand field parameters and NSH Hamiltonian parameters suggest tetragonal geometries of the complexes.     

固相配位化学反应研究——ⅩⅩⅩⅩⅠ.[Co(NH_3)_5(H_2O)]Br_3,[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应动力学研究

本文主要用气相色谱逸出气体分析方法,借助于红外、紫外可见漫反射谱等手段研究了[Co(NH_3)_5(H_2O)]Br_3、[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应,计算了失水与失氨的动力学参数,发现第一步反应失水生成一取代中间产物,其活化能与外加阴离子无关,为S_N1过程。第二步失氨反应活化能与中心离子M以及取代基Y有关,当M=Co(Ⅲ)时,反应体系的失氨活化能大小有下列顺序:Cl>Br>Ⅰ(E值分别为187、155、98kJ·mol~(-1)),M=Cr(Ⅲ)时则正好相反:Ⅰ>Br>Cl(E值分别为213、146、79 kJ·mol~(-1))。     

Phase Chemistry Investigation on Cr(NO3)3‐Met‐H2O System

The solubility property of the ternary of Cr(NO₃)₃‐Met‐H₂O has been investigated in the whole concentration by the phase equilibrium method, and the phase diagram has been constructed. From the phase diagram, the congruently soluble complexes Cr(Met)(NO₃)₃·2H₂O (D) and Cr(Met)₂(NO₃)₃·2H₂O (E) have been prepared and characterized by chemical analysis, elemental analysis, IR and TG‐DTG. Their combustion energies have been determined by a RBC‐type I precision rotating‐bomb calorimeter, and their standard enthalpies of formation, Δf, Hθ_m, have been calculated as (‐1842.01 ± 2.13) kJ·mol^?1 and (‐1136.16 ± 4.45) kJ·mol^?1, respectively.     

Effect of Al?H···H?O dihydrogen bond on the reaction between diphenylmethanol and pyrazolate‐bridged dialuminum complex. An ONIOM DFT/AM1 study

To elucidate the nature of the Al? H···H? O dihydrogen bond and its effect on the reaction between diphenylmethanol and pyrazolate‐bridged dialuminum complex, a theoretical study was carried out using the ONIOM(B3LYP/6‐31+G(d,p):AM1) method. Calculations indicate that this reaction is a two‐step process. The first step is nucleophilic addition and the resulting intermediate is stabilized by an Al? H···H? O dihydrogen bond. Topology analyses based on the “atoms‐in‐molecules” theory show that the Al? H···H? O dihydrogen bond in dialuminum intermediate is stronger than normal hydrogen bond. This step is not barrierless, which is contrary to the result predicted by using simplified model. The second step, eliminating a molecule of dihydrogen, requires an activation free energy of 9.9 kcal/mol in gas phase, which implies the simplified model underestimates the energy barrier of this elimination step. ONIOM calculations also show that, using the simplified model without zero‐point energy correction, the dihydrogen bonding strength has been underestimated and unreliable results have been obtained. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Cobalt(II) complexes of biologically active glutathione: spectroscopic and molecular modeling studies

Cobalt(II) complexes of reduced glutathione (GSH) of general composition Na[Co(L)(X)].nH2O (where H2L = GSH; X = Cl-, NO3-, NCS-, CH3CO2-, HCO2-, ClO4- and n = 0-4) have been synthesized and characterised by elemental analyses, vibrational spectra, electronic spectra, magnetic susceptibility measurements, thermal studies and molecular modeling studies. Electronic spectra indicate planar geometry for all the complexes. Infrared spectra indicate the presence of H2O molecules (except perchlorate complex) in the complexes that has been supported by TG/DTA. The room temperature magnetic moment values for all complexes lie in the range of 2.60-2.80 BM range indicating departure from spin only values due to second order Zeeman effect. Thermal decomposition of all the complexes proceeds via first order kinetics. The Na[Co(L)(Cl)].2H2O complex has the minimum activation energy and Na[Co(L)(CH3CO2)].3H2O has the maximum activation energy. The molecular modeling calculation for energy minimization optimizes geometry of the metal complexes.     

Zinc and Cobalt Aqua Complexes with Cucurbit[6]uril: Syntheses and Crystal Structures

Russian Journal of Coordination Chemistry - Supramolecular complexes [Zn(H2O)4(C36H36N24O12)](NO3)2 · 6.5H2O (I), [Zn(H2O)4-(C36H36N24O12)](NO3)2 · 7H2O (II), and...