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。     

含氮原子桥联吡咯基稀土金属双核配合物的合成及催化ε-己内酯的开环聚合反应（英文）

RE(CH_2SiMe_3)_3(THF)_2和1.5 equiv.(C_4H_3NHCH_2)_2NCH_3 (1)反应合成得到含氮原子桥联吡咯基稀土金属双核配合物[η~1:η~1:η~1-(C_4H_3NCH_2)_2NCH_3]RE{μ-η~5:η~5:η~1-(C_4H_3NCH_2)_2NCH_3}RE[η~1:η~1:η~1-(C_4H_3NCH_2)_2NCH_3](THF)[RE=Y(2),Er(3), Yb (4)],所得配合物经过核磁共振、红外和元素分析表征,配合物2和4经单晶X-Ray进一步确认结构.同时研究了稀土配合物作为单一组分催化剂催化ε-内酯的开环聚合反应.     

气液色谱法研究双—(O,O''''—二正辛基二硫代磷酸酯)合镍(Ⅱ)与五员杂环化合物加合反应的热力学性质

气液色谱法是研究酸碱相互作用热力学性质的有效方法之一,适合于气液表面化学反应的研究,可以得到一些用其他方法难以获得的热力学参数,丰富了表面化学领域的研究,具有重要的理论意义和应用价值。文献[1—4]利用气液色谱法测量了Ni[THDD]_2、Ni[(C_8H_(17)O)_2PS_2]_2与含氮、含氧有机碱加合反应的平衡常数、标准焓变和标准熵变值。作为酸碱加合反应研究的一部份,本文测定了Ni[C_8H_(17)O)_2PS_2]_2与五员杂环化合物呋喃、噻吩和吡咯反应的热力学参数。     

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。     

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

气液色谱法是研究酸碱相互作用热力学性质的有效方法之一。文献[1～3]利用气液色谱法测量了Ni(THDD)_2、Ni[(C_8H_(17)O)_2PS_2]_2与含氮有机碱加合反应的平衡常数、标准焓变和标准熵变值,得到了与光谱法相一致的结果。作为酸碱加合反应研究的一部分,本文测定了Ni[(C_8H_(17)O)_2PS_2]_2与醛类化合物的热力学参数。     

铍-铍金属链夹心配合物D_(4d)[Be_n(C_4H_4)_2]~(2-)及[Be_n(C_4H_4)_2]Li_2(n=2~8)（英文）

采用密度泛函理论方法(B3LYP和BP86)在6-311+G(d,p)基组水平上系统研究了新颖的铍-铍金属链夹心配合物D_(4d)[Be_n(C_4H_4)_2]~(2-)及[Be_n(C_4H_4)_2]Li_2(n=2~8)的几何结构、电子结构、成键特征及热力学稳定性。结果表明,具有交错式D4d对称性的D_(4d)[Be_n(C_4H_4)_2]~(2-)及[Be_n(C_4H_4)_2]Li_2为体系势能面上的真正极小。自然键轨道(NBO)、分子中的原子(AIM)及分子轨道分析表明,该系列夹心配合物中铍-铍间主要以共价键为主,而配体与铍-铍链之间则主要以离子键为主。核独立化学位移(NICS)分析表明配体在该系列配合物中具有π芳香性。稳定的夹心配合物锂盐[Be_n(C_4H_4)_2]Li_2(n=2~8)有望通过C4H4Li2/C5H-5配体交换反应进行制备,该系列配合物将进一步丰富多核夹心配合物研究领域。     

铀的三元协萃规律研究——HTTA-HPMBP-(C_8H_5)_4AsCl三元协萃高氯酸铀酰的机理

本文研究α-噻吩甲酰三氟丙酮(HTTA)、1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(HPMBP)与四苯基砷氯(C_6H_5)_4AsCl的氯仿溶液从高氯酸中萃取U(VI).该体系属螯合、离子缔合AAC类,其二元及三元协萃平衡常数分别为:logβ_(A_1C)=3.97[HTTA-(C_6H_5)_4AsCl];logβ_(A_2C)=4.86[HPMBP-(C_6H_5)_4AsCl];logβ_(A_1A_2C)=5.52[HTTA-PMBP-(C_6H_5)_4AsCl].用亚甲基蓝光度法测定了萃合物中ClO_4~-的存在,用斜率法确定二元协萃物组成为(C_6H_5)_4As~+[UO_2(ClO_4)(TTA)_2]~-和(C_6H_5)_4As~+[UO_2(ClO_4)(PMBP)_2]~-,三元协萃配合物为(C_6H_5)_4As~+[UO_2(ClO_4)(TTA)(PMBP)]~-.     

含柔性希夫碱配体的双核稀土配合物的制备、结构及发光性能研究

分别以柔性长链希夫碱N,N'-双(3-甲氧基-水杨醛)-1,7-庚二胺(H_2L~1)与N,N'-双(3-甲氧基-水杨醛)-1,9-壬二胺(H_2L~2)为配体,合成了4个具有纳米分子尺寸的双核稀土配合物[Ln_2(H_2L~1)_2(OAc)_4]·2(CF_3SO_3)(Ln=Pr(1),Eu(2))和[Ln_2(H_2L~2)_2(OAc)_4]·2(CF_3SO_3)(Ln=Pr(3),Eu(4))。晶体结构表明,在这些配合物中,长链希夫碱配体均表现出"伸展式"的配位方式,并将两个稀土离子螯合在配合物结构的中央。发光性能研究表明,配合物1~4均表现出希夫碱配体部分的可见区发光。     

2,6—二乙酰吡啶类双希夫碱配合物的研究——Ⅲ.Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)配合物的合成和表征

制备了由2,6—二乙酰吡啶和肼基硫代甲酸酯衍生的希夫碱C_5H_3N[CH=NNHC(S)XR]_2(X=S,R=CH_3、C_6H_5CH_2;X=O,R=C_6H_5CH_2).离析出类型为MC_5H_3N[CH=NN=C(S)XR]_2(M=Co~(2+)、Ni~(2+)、Zn~(2+)、Pb~(2+)和Cd~(2+))的希夫碱配合物.配合物为元素分析、红外、可见—紫外光谱以及磁化率测量所表征.结果指出:上述希夫碱均为N_3S_2型五齿配体.     

三价铬丙二酸配合物[Cr(C_3H_2O_4)(H_2O)_4][Cr(C_3H_2O_4)_2(H_2O)_2]·4H_2O的合成、晶体结构及性质研究

在三重桥氧三核铬羧酸配合物的系列研究中,采用与铬的一元羧酸配合物类似的实验条件,以丙二酸为配体合成了不同构型的配合物[Cr(C_3H_2O_4)(H_2O)_4)][Cr(C_3H_2O_4)_2(H_2O)_2]·4H_2O,通过X射线衍射测定了其单晶结构,并对-COO的配位方式作了讨论,还研究了配合物的红外光谱、拉曼光谱、紫外可见光谱、质谱、磁化率等性质,探讨了性质与结构的关系,并由此论证了二元羧酸和铬形成的双齿螯合构型化合物的稳定性.     

Ternary systems LiBr-Li2MoO4-Li2WO4 and LiF-Li2MoO4-Li2WO4

The ternary systems LiBr-Li₂MoO₄-Li₂WO₄ and LiF-Li₂MoO₄-Li₂WO₄ were studied by differential thermal analysis. The fields of crystallizing phases are delimited, and di- and monovariant equilibria for surfaces and monovariant curves are described.     

Kristallstrukturen von MgCr2O4-Typ Li2VCl4 und Spinell-Typ Li2MgCl4 und Li2CdCl4

Crystal Structures of MgCrO₄-type Li₂VCl₄ and Spinel-type Li₂MgCl₄ and Li₂CdCl₄ The crystal structures of the ternary lithium chlorides Li₂MCl₄ (M = Mg, V, Cd) have been determined firstly by X-ray single-crystal experiments. Li₂MgCl₄ and Li₂CdCl₄ crystallize in an inverse spinel structure (space group Fd3 m, Z = 8, a = 1 040.1(2) and 1 062.06(9) pm, structural parameters u = 0.25699(2) and 0.2550(1), R = 1.7 and 3.7% for 218 and 211 unique reflections). The Li? Cl distances of the tetrahedrally coordinated Li⁺ ions are significantly greater than calculated with Shannon's crystal radii ( > 238 ± 1 instead of 233 pm). Contrary to the results of X-ray powder data reported in the literature, Li₂VCl₄ crystallizes in the distorted spinel structure of MgCr₂O₄ type (space group F4 3m, Z = 8, a = 1 037.49(2) pm, R = 5.9% for 217 unique reflections). The decrease of the site symmetry of the octahedrally coordinated ions (V²⁺, Li⁺) from 3 m to 3m resulting in contracted and widened tetrahedral M₄ entities of the spinel structure is obviously caused by V? V metal—metal bonds (shortest V? V distance 366.2(7) pm).     

Zur Kenntnis der Chlorid-Spinelle Li2MgCl4, Li2MnCl4, Li2FeCl4, Li2CdCl4

About the Chloride Spinels Li₂MgCl₄, Li₂MnCl₄, Li₂FeCl₄, Li₂CdCl₄ FIR, Raman, and X-ray data of the spinel type chlorides Li₂TCl₄ (T = Mg, Mn, Fe, Cd) are presented. The vibrational spectra indicate that there is no 1:1 ordering on the octahedral sites of the lattice. Both DTA measurements and high temperature X-ray photographs show that the chloride spinels undergo a reversible phase transition to a cubic high temperature defect structure at 535°C (Li₂MgCl₄), 460°C (Li₂MnCl₄) and 385°C (Li₂CdCl₄), which has unit cell dimensions two times smaller than the spinel lattice. Disordering of the lithium sublattice still begins at much lower temperatures, as measurements of the electric conductivity indicate.     

Darstellung und Struktur von BaAl2Se4, BaGa2Se4, CaGa2Se4 und Caln2Te4

Preparation and Crystal Structure of BaAl₂Se₄, BaGa₂Se₄, CaGa₂Se₄, and CaIn₂Te₄ The new compounds BaAl₂Se₄, BaGa₂Se₄, CaGa₂Se₄ and CaIn₃Te₄ crystallize with constants see “Inhaltsübersicht”. The structures are strongly related to the TlSe structure.     

Li~2SO~4-MgSO~4、LiSO~4-Li~4SiO~4体系的研究

本文用X射线衍射(高温、室温)和热分析(DTA、DSC、TGA)等方法测定了Li~2SO~4-MgSO~4和Li~2SO~4-Li~4SO~4体系相图,并研究了化合物的性能和晶体结构。Mg~4Li~2(SO~4)~5在840℃由包晶反应形成,它在105℃分解为Li~2SO~4为基的固溶体和MgSO~4.在105℃反应时,形成每摩尔的Mg~4Li~2(SO~4)~5吸热2.57kJ,反应激活能为173.5kJ/mol. Mg~4Li~2(SO~4)~5属正交晶系,在180℃的点阵常数α=8.577A,b=8.741A, c=11.918A, 可能的空间群为P222或Pmmm,Z=2。Li~8-2x(SiO~4)~2-x(SO~4)~x是在953℃由包晶反应形成的新相.随着温度的降低,相区扩大,在室湿x=0.96-0.58.该相属正交晶系,空间群为Pmmn,Z=2.晶体的点阵常数在x=0.8时有一定最大值,a=5.002A,b=6.173A, c=10.608A.Li~g-2x(SiO~4)~2-x(SO~4)~x在空气中能吸收7.6wt%的水蒸汽和其他气体,脱水温度高于350℃,水份的吸脱不改变晶体结构,与沸石分子筛具有相似性质,脱水激活能为171.5kJ/mol.熔化后的Li~2SO~4-MgSO~4和Li~2SO~4-Li~4SiO~4试样以10℃/min速率降温,分别形成亚稳态共晶体系。     

Studies on Li2SO4-MgSO4 and Li2SO4-Li4SiO4 systems

The phase equilibria as well as the properties and crystal structures of the compounds formed in both Li₂SO₄-MgSO₄ and Li₂SO₄-Li₄SiO₄ systems have been studied by means of x-ray diffraction technique (at high and room temperatures) as well as by the thermal analyses (DTA, DSC, TGA, etc.). In Li₂SO₄-MgSO₄ system there exists a compound Mg₄Li₂(SO₄)₅ formed by peritectic reaction at 840°C and decomposed at 105°C into the Li₂SO₄-base solid solution and MgSO₄ · Mg₄Li₂(SO₄)₅ and Li₂SO₄-base solid solution conduct an eutectic reaction at 663°C with the composition of eutectic point lying in 22 mol% MgSO₄. The solubility of MgSO₄ in Li₂SO₄ is a little smaller than 10 mol% while at the same time the Li₂SO₄ phase transition temperature decreases from 574 to 560°C On the other hand, no noticeable solid solubility of Li₂SO₄ in MgSO₄ has been observed. The reaction is an endothermal one and its heat of formation is 2.57 kJ/mol. The activation energy of the reaction calculated by thermal peak displacement method at various heating rates is 173.5 kJ/mol (1.80 ev). The crystal Mg₄Li₂(SO₄)₅ belongs to orthorhombic system with lattice parameters at 180°C: a = 8.577, b=8.741, c= 11.918 Å. The space group seems to be either P222 or P mmm. Assuming that there are two formula units in a unit cell, the density calculated is then 2.20 g/cm³ very close to that of Li₂SO₄ or MgSO₄. Meanwhile, in Li₂SO₄-Li₄SiO₄ system a new phase Li_8-2x(SiO₄)_8-x(SO₄)_x is formed by peritectic reaction at 953°C with a range of composition x=0.96 ?0.58. The crystal belongs to ortho-rhombic system with lattice parameters at x=0.8: a = 5.002, b= 6.173 and c=10.608Å. The density observed is 2.31 g/cm³ and there are 2 formula units in an unit cell. It is shown from the measurements of piezoelectric and laser SHG coefficients of the crystal that the crystal posseses a symmetrical center with the space group belonging to P mmn. The lattice parameter c has a maximum at x=0.8. In the air Li_8-2x(SiO₄)_2-x(SO₄)_x can absorb 7.6 wt% water vapour and other gases which can only be desorbed by heating it at a temperature above 350°C. Neither absorption nor desorbtion can change its crystal structure, a characteristic similar to that of zeolite molecular sieve. The dewater activation energy of Li_8-2x(SiO₄)_2-x(SO₄)_x is 171.5 kJ/mol. Li_8-2x(SiO₄)_2-x(SO₄)_x and Li₄SO₄ bring about an eutectic reaction at 823°C with its eutectic composition being 12 mol% Li₄SiO₄. No observable solubility of Li₄SiO₄ in Li₃SO₄ has been noticed. The solubility of Li₂SO₄ in Li₄SiO₄ is approximately equal to 5 mol%. With Li₂SO₄ being dissolved in, the phase transition temperature of Li₄SiO₄ is decreased. After being fused, the specimens Li₃SO₄-MgSO₄ and Li₂SO₄-Li₄SiO₄ are cooled at a rate of 10°C/min, their metastable eutectic systems are resulted respectively.     

Synthesis and Characterization of Gd2[Pt2(SO4)4(HSO4)2](HSO4)2

Red single crystals of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ (triclinic, , Z = 1, a = 844.02(9), b = 908.50(9), c = 939.49(8) pm, α = 107.73(1)°, β = 112.10(1)°, γ = 103.53(1)°) were obtained by the reaction of [Gd(NO₃)(H₂O)₇][PtCl₆]·4H₂O with sulfuric acid at 320 °C in a sealed glass ampoule. In the crystal structure, Pt₂ dumbbells are coordinated by four chelating sulfate groups and two monodentate hydrogensulfate ions. Two further HSO₄^? ions are not bonded to the Pt₂ dumbbell. The Gd³⁺ ions are eightfold coordinated by oxygen atoms. The IR data of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ are typical for these type of compounds. The thermal decomposition of the compound leads to elemental platinum and Gd₂O₃.     

Four-component system LiF-K2WO4-CaF2-CaWO4

The four-component system LiF-K₂WO₄-CaF₂-CaWO₄ has been studied by physicochemical analysis. The phase and crystallization trees have been predicted a priori and have been experimentally verified by constructing a topological model of the phase diagram and by solving the equations expressing the general law of liquidus surface formation. The heat-storage properties of the eutectic compositions are evaluated.     

Photolyse von 2, 2, 4, 4-Tetramethylcyclobutanon-Derivaten

The photochemical reactions of the 2, 2, 4, 4-tetramethylcyclobutanones 1–6 carrying various substituents in 3-position were investigated. The major reaction in alcoholic solution or in the presence of other protic compounds was the formation of the semicyclic acetals 7–12 . Parallel to this reaction decarbonylation occurred, leading to stable cyclopropane derivatives in some cases, depending on the substituents present. Cyclopropanes with an exocyclic double bond underwent ring opening easily or, in case of an exocyclic carbon-nitrogen double bond, added alcohol, thus forming cyclopropane O, N-ketals. Alkyl-acyl biradicals are proposed as common intermediates for both photoreactions. Based on analogy to similar photoreactions reported in the literature, the formation of the semicyclic acetals is assumed to involve a carbene intermediate.