气液色谱法测定双-(4,6-二异丙基水杨酸)合铜(Ⅱ)与脂肪胺和醇加合反应的热力学性质

用气液色谱法,在不同的温度下,测定了以α-甲基萘作为固定液时,路易斯碱脂肪胺和醇的溶解平衡常数K_R~0,以及它们与作为路易斯酸的过渡金属配合物双-(4,6-二异丙基水杨酸)合铜(Ⅱ)相互作用的表观分配常数K_R和加合反应的平衡常数K_1。再根据热力学公式: 进一步求出了加合反应的焓变ΔH和熵变ΔS。     

气液色谱法测定一些Lewis碱与Ni(ENAC).H2O的加合常数

配位不饱和的过渡金属配合物作为一种Lewis酸(A)可以进一步和Lewis碱(B)作用,形成配合物AB.许多生化过程和催化过程都与这种类型的配合物有关.曾经用光谱和量热等方法研究过配位键A—B的强弱.本文在Drago等人的工作基础上,利用气液色谱法     

气液色谱法研究Ni[(C_8H_(17)O)_2PS_2]_2与脂肪胺加合反应的热力学性质

气液色谱法是研究非电解质溶液热力学性质的一个有效方法,可以测定非水溶液中有机化合物的缔合常数,研究氢键形成过程的热力学及过渡金属配合物与路易斯碱的加合反应热力学。本文探讨了该方法的适用范围,及酸碱加合反应的热力学性质;测定了Ni[(C_8H_(17)O)_2PS_2]_2为路易斯酸与脂肪胺系列发生加合反应的热力学性质。     

气液色谱法测定双-(4,6-二异丙基水杨酸)合铜(Ⅱ)与脂肪胺和醇加合反应的热力学性质

用气液色谱法,在不同的温度下,测定了以α-甲基萘作为固定液时,路易斯碱脂肪胺和醇的溶解平衡常数K_R⁰,以及它们与作为路易斯酸的过渡金属配合物双-(4,6-二异丙基水杨酸)合铜(Ⅱ)相互作用的表观分配常数K_R和加合反应的平衡常数K₁。再根据热力学公式: -RlnK₁=ΔH1/T-ΔS 进一步求出了加合反应的焓变ΔH和熵变ΔS。     

气液色谱法测定脂肪醇和脂肪胺与Ni〔CF_3COCHC(C_4H_4S)=NCH_2〕_2加合反应的热力学参数

本文用气液色谱(GLC)法的保留值方法测定作为Lewis碱的脂肪醇和脂肪胺在固定液角鲨烷中的溶解平衡常数K_R~+、碱与作为Lewis酸的辣Ni[CF_3COCHC(C_4H_4S)=NCH_2]_2配合物的表观平衡常数K_R以及碱的真实加合常数K_1,以LnK_1对1/T作图求出了加合作用的热力学函数△H和△S值.它们和醇及胺中碳数n间存在线性关系。K_R~+和K_R值随碳数的增加而增大,K_1值随碳数的增加而减小。所有加合反应都是热的,熵值随着碳数的增加而减小。     

双-[N-(4-取代苯基)-水杨醛亚胺]合锌(Ⅱ)的晶体结构

许多过渡金属与席夫碱的配合物具有生物活性,研究这类化合物的晶体结构很重要,我们曾经报道了双—[N—4—取代苯基—水杨醛亚胺]含钴(Ⅱ)配合物的晶体结构,为了进一步研究过渡金属离子与席夫碱配合物结构与性能的关系,本文报道双—[N—(4—取代苯基)—水杨醛亚胺]合锌的晶体结构。     

气液色谱法研究一些五员杂环和Ni[CF_3COCHC(C_4H_4S)=NCH_2]_2加合反应的热力学性质

用气液色谱法研究过一系列作为Lewis碱(B)的有机配体和作为Lewis酸(A)的配合物之间的加合作用.研究较多的碱已有脂肪醇、醚、酮、醛、脂及胶等.对生物体系中广为存在的杂环配体碱的工作还很少.本文着重研究噻吩,呋喃和吡咯这类小分子杂环配体和Ni[CF_3COCHC(C_4H_4S)=NCH_2]_2(以下简称A)配合物的加合反应. Ni[CF_3COCHC(C_4H_4S)=NCH_2]_2的合成参考文献.固定液角鲨烷系英国进口,     

微量热法研究 [Cu(phen)2]~(2 )、[Cu(bpy)_2]~(2 )与DNA的作用

用微量热法对菲咯啉合铜（ [Cu(phen)2]2＋）和联吡啶合铜（ [Cu(bpy)2]2＋）与小牛胸腺 DNA的相互作用进行了研究,依据 McGhee-Von Hippel邻近排斥方程确定了结合反应的平衡常数 K、结合位点距离 n及热力学参数Δ rHm、Δ rGm和Δ rSm。结果表明这两种铜的配合物与 DNA之间均可形成稳定的三元配合物,且反应为熵驱动过程, DNA与这些配合物的键合过程中同时存在插入和静电作用两种模式,插入作用的强弱与金属配合物中配体的平面性质有关。     

气液色谱法研究双-(O,0′-二正辛基二硫代磷酸酯)合镍(Ⅱ)与酮类加合反应的热力学性质

二烷基二硫代磷酸酯及其过渡金属配合物具有强杀菌性能及抑制酶水解作用,可以用作石油添加剂和高聚物防老剂,又是一类优良的萃取剂,用于钴镍、钴锰等的萃取分离^[1-2]。二硫代磷酸酯的金属盐与含氮、含氧的有机碱形成的加合物在液-液萃取中起着重要作用^[3],因此这类配物合的加合作用受到了广泛的注意。     

N,N’-双(2-羟基-4-甲氧基二苯酮)乙二亚胺合铜(Ⅱ)、镍(Ⅱ)、钴(Ⅱ)配合物的合成

水杨醛 Schiff碱类配合物的研究已有很多报道[1,2 ] ,而二苯酮 Schiff碱类配合物报道则很少 .另外 ,利用固液相反应合成配合物的报道也不多见 .本工作是将 2 -羟基 - 4-甲氧基二苯酮与乙二胺缩合 ,合成 Schiff碱 ,进而与过渡金属盐通过固液相反应合成配合物 ,以便探讨新化合物的护肤防晒性能 .我们发现 ,配合物对紫外光吸收强度可增加 3～ 4倍 ,具有较好的防晒效果 .EA- 1 0 6型元素分析仪 ;理学 D/ max- YB X射线衍射仪 ,Cu Kα射线 (λ=0 .1 5 4 nm) ,Ni单色器 ,电压 40 k V,电流 40 m A,扫描速度 2°/ min,室温收集 3～ 80°( 2θ)…     

Reactions of Lewis bases with tetrakisdiphenylamide uranium(IV)

The coordinatively unsaturated uranium(IV) complex U[N(C₆H₅)₂]₄ has been prepared via the stoichiometric reaction of diphenylamine with [(Me₃Si)₂N]₂ H₂. U[N(C₆H₅)₂]₄ coordinates Lewis bases such as Et₂O, THF, pyridine or (EtO)₃PO, based on electronic absorption spectroscopy and ¹H NMR studies. Exchange between U[N(C₆H₅)₂]₄ and U[N(C₆H₅)₂]₄(L), where L is THF or pyridine, is rapid on the NMR time-scale between 307 and 323 K. Measurement of equilibrium constants for L = THF provides ΔH and ΔS values of −60 kJ mol⁻¹ and −1.8 × 10² J K⁻¹ mol⁻¹, respectively. U[N(C₆H₅)₂]₄ coordinates and binds (EtO)₃PO much more tightly (K_eq = & > 10⁴ M⁻¹) than THF or pyridine with the exchange rate between U[N(C₆H₅)₂]₄ and U[N(C₆H₅)₂]₄[OP(OEt)₃] being close to the NMR time-scale.     

Synergic Extraction of Uranium Thiocyanate by the Ternary System of ABC Species Composed of PMBP-TBP-(C6H5)4AsCI

The synergic extraction of uranyl thiocyanate with binary system of 1-phenyl-3-methy1~4-benzoylpyrazolone-5 (PMBP)and tributyl phosphate(TBP)or tetraphenylarsonium chloride [(C6H5)4AsCl] and ternary system of PMBP-TBP-(C6H5 )4AsCl was studied.There was an obvious synergic effect of uranium (VI)from thiocyanate medium in binary and ternary systems.The formation of a ternary extracted complex,(C6H5)4AsUO2.(NCS)A2 TBP,was confirmed by the slope method.A method was first proposed for the calculation of the equilibrium constant of ternary synergic reaction.     

Pyrolysis mechanism of carbon matrix precursor cyclohexane(III)—pyrolysis process of intermediate 1-hexene

The pyrolysis mechanism of important intermediate 1-hexene of carbon matrix precursor cyclohexane was studied theoretically. Possible reaction paths were designed based on the potential surface scan and electron structure of the initial C–C bond breaking reactions. Thermodynamic and kinetic parameters of the possible reaction paths were computed by UB3LYP/6-31+G* at different temperature ranges. The results show that 1-hexene pyrolyzes at 873 K. When below 1273 K, the major reaction paths are those that produce C₃H₄, and above 1273 K, the major reaction paths are those that produce C₃H₃ from the viewpoint of thermodynamics. From the viewpoint of kinetics, the major product is C₃H₃, it results from the pyrolysis reaction of 1-hexene cracking bond C₃–C₄ and generating C₃H₅ and C₃H₇ with the activation energy ΔE₀^≠θ=296.32 kJ/mol. Kinetic results also show that product C₃H₄ accompany simultaneously, which is the side reaction starting from the pyrolysis of 1-hexene forming C₄H₇ and C₂H₅ with the activation energy of 356.73 kJ/mol. When reaching 1473 K, the rate constant of the rate-determining steps of these two reaction paths do not show much difference, which means both the reaction paths exist in the pyrolysis process at the high temperature. The above results are basically in accordance with mass spectrum analysis and far more specific.     

Interaction of half-sandwich alkylmolybdenum(III) complexes with B(C6F5)3. The X-ray structure of [CpMo(η-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3]

The reactions of the half-sandwich molybdenum(III) complexes CpMo(η⁴-C₄H₄R₂)(CH₃)₂, where Cp=η⁵-C₅H₅ and R=H or CH₃, with equimolar amounts of B(C₆F₅)₃ have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe₃. The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η⁴-C₄H₆)(μ-Cl)(μ-CH₂)(O)MoCp][CH₃B(C₆F₅)₃], indicate that the borane attack has occurred at the methyl position.     

Synthesis of methyltrioxorhenium(VII) arylamine complexes and mono- and bis(ortho)-chelated arylaminorhenium(VII) trioxides

From the reaction of MeReO₃ with the neutral arylamine C₆H₅CH₂NMe₂ and the aryldiamine C₆H₄(CH₂NMe₂)₂−1,3, have been isolated in good yields the 1/1 adduct complex [MeReO₃ · C₆H₅CH₂NMe₂], 1, and the 2/1 adduct complex [(MeReO₃)₂ · C₆H₄(CH₂NMe₂)₂− 1,3], 2, respectively. The X-ray molecular structure of 2 shows that both rhenium centres have a trigonal bipyramidal geometry and in the axial positions of each rhenium centre are one of the NMe₂ units of the aryldiamine ligand and a methyl group. The mono(ortho)-chelated arylaminorhenium trioxide complex [ReO₃(C₆H₄CH₂NMe₂−2], 3, can be synthesized by a transmetallation reaction of ClReO₃ with [ZnC₆H₄CH₂NMe₂−2₂] in a 2:1 molar ratio. In a similar way the bis(ortho)-chelated arylaminorhenium trioxide complex [ReO₃C₆H₃(CH₂NMe₂)₂−2,6], 4, can be synthesized by addition of a mixture of [Li₂C₆H₃(CH₂NMe₂)₂−2,6₂] and ZnCl₂ to ClReO₃. Complexes 3 and 4 have been isolated as white solids in 66% and 81% yields respectively. The rhenium centre in complex 4 has a bicapped tetrahedral geometry in which the monoanionic C₆H₃(CH₂NMe₂)₂−2,6⁻ ligand is pseudo-facially bonded with a characteristic N1-Re-N2 angle of 107.7(3)°, a Re-C_ipso bond length of 2.112(11) Å and Re-N1 and Re-N2 bond lengths of 2.518(9) Å and 2.480(8) Å respectively.     

Predicting of Covalent Organic Frameworks for Membrane-based Isobutene/1,3-Butadiene Separation: Combining Molecular Simulation and Machine Learning

Efficient separation of C4 olefins is of critical importance and a challenging task in petrochemical industry. Covalent organic frameworks(COFs) could be used as promising candidates for membrane-based isobutene/1,3-butadiene(i-C₄H₈/C₄H₆) separation. Owing to large amounts of COFs appearing, however, the rapid prediction of optimal COFs is imperative before experimental efforts. In this work, we combine molecular simulation and machine learning to study COF membranes for efficient isolation of i-C₄H₈ over C₄H₆. Using molecular simulation, four potential COF membranes, which possess both high membrane performance score (MPS) value and moderate membrane selectivity were screened out and the mechanism of membrane separation further revealed is an adsorption dominated process. Further, random forest(RF) model with high prediction accuracy(R²>0.84) was obtained and used for elucidating key factors in controlling the membrane selectivity and i-C₄H₈ permeability. Ultimately, the optimal COF features were obtained through structure-performance relationship study. Our results may trigger experimental efforts to accelerate the design of novel COFs with better i-C₄H₈/C₄H₆separation performance.     

Mesogenic behaviour of (4-alkoxybenzylideneamino)bromobenzene, (4-alkoxybenzylideneamino)benzenethiols, and thiolatonickel complexes of the thiols

The synthesis, characterization and mesogenic properties of Schiff base compounds arising from the reaction of 4-alkoxybenzaldehydes with 4-aminothiophenol or 4-bromoaniline are described. Whereas the Schiff base thiol with two benzene rings in the molecule, HSC₆H₄NC(H)C₆H₄OC₁₆H₃₃ (2), is non-mesogenic, the bromo analogue, BrC₆H₄NC(H)C₆H₄OC₁₆H₃₃ (3), is mesogenic. The introduction of a third benzene ring into the molecular architecture of 2 and 3 produced thiol- and bromo-Schiff base compounds, HSC₆H₄NC(H)C₆H₄OC(O)C₆H₄OC₁₆H₃₃ and BrC₆H₄NC(H)C₆H₄OC(O)C₆H₄OC₁₆H₃₃, respectively, that are both mesogenic. The thiol compounds react with nickelocene to form [(η ⁵-C₅H₅)Ni(μ ₂-SC₆H₄NC(H)C₆H₄OC₁₆H₃₃)]₂ and [(η ⁵-C₅H₅)Ni(μ ₂-SC₆H₄NC(H)C₆H₄OC(O)-C₆H₄OC₁₆H₃₃)]₂, but the nickel complexes are not mesogenic.     

C59(C6H4OCH3)N的结构、光谱和二阶非线性光学性质的理论研究

用INDO系列方法对由(C₅₉N)₂和苯甲醚合成的衍生物C₅₉(C₆H₄OCH₃)N进行了理论研究,得到了分子的稳定构型.结果表明,C₅₉(C₆H₄OCH₃)N具有C_s对称性.以优化构型为基础讨论了分子的UV-Vis光谱、NMR谱线数,结果与实验符合得很好.本文还计算了C₅₉(C₆H₄OCH₃)N的二阶非线性光学系数β_μ,结果表明这种物质具有较大的二阶非线性光学系数.     

Binary systems of C60 with positional isomers 1,2- and 1,3-C6H4Br2

Thermodynamic properties of binary systems of C₆₀ with 1,2- and 1,3-dibromobenzenes have been studied by means of differential scanning calorimetry (DSC). Solid solvates with the compositions C₆₀3(1,2-C₆H₄Br₂); C₆₀2(1,3-C₆H₄Br₂) and C₆₀0.6(1,3-C₆H₄Br₂) have been found. The solvates have been characterised by their enthalpies and temperatures of incongruent melting transition and in part by X-ray powder data. It has been shown that positional isomers 1,2- and 1,3- of the substituted benzenes formed two series of “typical” phase diagrams. Solubility behaviour of C₆₀ in positional isomers has been discussed.     

Synthesis and crystal structures of (C8h8)Nd(C5H9C5H4) (THF)2 and [(C8H8)Gd(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)2]

LnCl₃ (Ln=Nd, Gd) reacts with C₅H₉C₅H₄Na (or K₂C₈H₈) in THF (C₅H₉C₅H₄ = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C₅H₉C₅H₄)LnCl₂(THF)_n (orC₈H₈)LnCl₂(THF)_n], which further reacts with K₂C₈H₈ (or C₅H₉C₅H₄Na) in THF to form the litle complexes. If Ln=Nd the complex (C₈H₈)Nd(C₅H₉C₅H₄)(THF)₂ (a) was obtained: when Ln=Gd the 1 : 1 complex [(C₈H₈)Gd(C_%H₉)(THF)][(C₈H₈)Gd(C₅H₉H₄)(THF)₂] (b) was obtained in crystalline form.

The crystal structure analysis shows that in (C₈H₈)Ln(C₅H₉C₅H₄)(THF)₂ (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η⁵), cyclooctatetraenyl (η⁸) and two oxygen atoms from THF are coordinated to Nd³⁺ (or Gd³⁺) with coordination number 10.

The centroid of the cyclopentadienyl ring (Cp′) in C₅H₉C₅H₄ group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd³⁺ (or Gd³⁺). In (C₈H₈)Gd(C₅H₉C₅H₄)(THF), the cyclopentyl-cyclopentadienyl (η⁵), cyclooctatetraenyl (η⁸) and one oxygen atom are coordinated to Gd³⁺ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd³⁺, which is almost in the plane (dev. -0.0144 Å).