三种六氯铈(Ⅳ)酸有机盐的研究

合成了2,6-二甲基-γ-吡喃酮、咪唑和吡啶铈(Ⅳ)的氯化物,化学式为(C₇H₈O₂H)₂CeCl₆、(C₃H₄N₂H)₂CeCl₆和(C₄H₉NH)₄CeCl₈.采用差热、热重分析法比较了上述三种化合物的热稳定性,并配合以电导、红外、紫外光谱等手段进行了结构分析.     

新型金属-双二硫杂戊烯(M-BDT)配合物的合成、表征及X射线的指标化

合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH₃)₄N]₂[Ni(C₅S₉)₂](1),[(C₂H₅)₄N]₂·[Ni(C₅S₉)₂](2),[(C₄H₉)₄N]₂[Ni(C₅S₉)₂](3),[(C₆H₅)(CH₃)₃N]₂[Ni(C₅S₉)₂](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2.     

有机磷杀虫剂的研究——Ⅶ.某些苯基对位取代硫代膦酸酯的合成

1.制备一些新型的硫代膦酰氯,其中R'为C₆H₅,R"为C₂H₅O,C₂H₅,(CH₃)₂N,(C₂H₅)₂N,C₂H₅S等。     

硝酸铈(Ⅳ)与四氧二氮环醚配合物

本文报道通过中间配合物Ce(OPPh₃)₂(NO₃)₄与1,7,10,16-四氧-4,13-二氮杂环十八烷作用制得一组成为Ce(C₁₃H₂₆N₂O₄)(NO₃)₄·2.5(CH₃COCH₃)的黄色固体配合物。该配合物在空气中稳定,在大多数有机溶剂中不溶解,但可溶于DMSO中。运用电导、波谱技术对该配合物的性质进行了研究。     

(C26H40N2O4)[Ln(NO3)5H2O]的合成及其铕缔合物的晶体结构

合成了4个新型的稀土化合物(C₂₆H₄₀N₂O₄)[Ln(NO₃)₅H₂O](Ln=Pr,Nd,Sm,Eu),采用元素分析和红外光谱表征,用四圆衍射仪测定了其中(C₂₆H₄₀N₂O₄)[Eu(NO₃)₅H₂O]的晶体结构,属三斜晶系,P1空间群,晶胞参数:α=0.9100(4)nm,b=1.3560(3)nm,c=1.6463(4)nm;α=68.62(2)°,β=74.84(3)°,γ=87.50(2)°;Z=2.中心铕离子由5个硝酸根的10个氧原子和1个水分子中的氧原子配位,配位数是11.1,7,10,16-四氧-4,13-二氮杂-N,N'-二苄基环十八烷(N,N'-二苄基穴醚(2,2))未参与配位.     

系列Ln(Ⅲ)配位聚合物(Ln=Eu,Sm,Tb,Pr,Gd)的合成及其荧光分析

采用水热法合成了4个具有1D结构的Ln(Ⅲ)配位聚合物,[Eu₂(C₉H₇O₂)₆(C₉H₇O₂H)(C₂H₅OH)]n(1)、[Sm(C₉H₇O₂)₃]n(2)、[Tb(C₉H₇O₂)₃]n(3)和[Gd(C₉H₇O₂)₃]n(4)(C₉H₈O₂=肉桂酸)。 通过X射线单晶衍射确定了它们的结构。 这4个Ln(Ⅲ)配合物中,Ln(Ⅲ)的配位数均为9,桥配体均为肉桂酸根,但其配位方式有差异。 对配合物进行了IR、UV-Vis-NIR和荧光光谱等表征。 分析了各配合物的荧光发射,结果表明,在可见区,配合物1发射较明显的红光,配合物2、3发射绿光,配合物4发射蓝光,但很弱。 讨论了具有刚柔相混杂性质的肉桂酸配体对配位聚合物的构筑及稀土离子发光的影响。     

亚乙基桥联双茚锆、铪配合物的合成及催化丙烯选择性齐聚研究:茚环3-位取代基的影响

设计并合成了12个亚乙基桥联双茚类锆、铪配合物meso-/rac-1～7[ansa-C₂H₄-(3-R-4,7-Me₂-C₉H₃)₂MCl₂:M=Zr R=ⁿBu (meso-/rac-1),ⁱPr (meso-2),CH₂Cy (meso-/rac-3),Bn (meso-/rac-4),CH₂C₆H₄(4-CH₃)(meso-/rac-5);M=Hf,R=CH₂C₆H₄(4-CH₃)(meso-/rac-7);ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-(CH₂)₃]C₉     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了3个有机锡9-芴酮-4-甲酸酯:三苯基锡9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)](1)、三环己基锡9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)](2)和三(2-甲基-2-苯基丙基)锡9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)](3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗...     

双(正-辛基硫醚)乙烷对钯的萃取及其机理的研究

本文研究了双(正-辛基硫醚)乙烷[C₈H₁₇S(CH₂)₂SC₈H₁₇]对钯的萃取;讨论了盐酸浓度、稀释剂对萃取钯的影响;并且通过等克分子系列法、饱和法、Asmus法、固态络合物的化学分析及核磁共振谱,红外光谱的研究,确定了萃合物的组成和结构。     

含有酯基及酰胺基柔链的苯并菲盘状液晶的合成、分子间氢键对柱状介晶性的影响

合成了三个系列, 共二十四个有两种不同软链的对称和非对称苯并菲盘状液晶化合物, C₁₈H₆(OR)₃- (OCH₂COOEt)₃, C₁₈H₆(OR)₃(OCH₂COOBu)₃, C₁₈H₆(OR)₃(OCH₂CONHBu)₃, 其中R＝C₅H₁₁, C₆H₁₃, C₇H₁₅, C₈H₁₇. 化合物通过柱层析纯化, 结构通过¹H NMR, IR, 元素分析等确证. 化合物热稳定性通过TGA测定, 并显示出较高的热稳定性. 通过偏光显微镜和差视扫描量热法对这些化合物的热致液晶性进行了研究. 结果显示: 对于苯并菲液晶化合物C₁₈H₆(OR)₃(OCH₂COOEt)₃, 非对称性化合物较之对称异构体化合物有更低的熔点和更高的清亮点, 因而非对称性化合物有更宽的介晶温度范围. 对于分子中含有酰胺基的苯并菲液晶化合物C₁₈H₆(OR)₃(OCH₂CONHBu)₃, 对称化合物有比非对称异构体更高的清亮点和更有序的六方柱状介晶相, 且其与具有同样软链长度的分子中不含酰胺基的化合物系列C₁₈H₆(OR)₃(OCH₂COOBu)₃相比较, 由于柱内分子间氢键的形成, 不仅有更高的熔点和清亮点, 而且有更丰富的柱状介晶相.     

Theoretical study of the structures and properties of cyclic nitramines: Tetranitrotetraazadecalin (TNAD) and its isomers

Density Functional Theory (DFT) was employed to study the geometries, electronic structures, infrared vibrational spectra, and thermodynamic properties of seven isomeric cyclic nitramines of C₆H₁₀N₈O₈ (i.e., TNAD and its six isomers) at the B3LYP/6‐31G* level of theory. The experimental results available for TNAD were used to determine the reliability of the DFT method for generating structural and IR spectroscopic values for these molecular systems. The relative stabilities of the conformers were evaluated from the energy differences of the structures. Detonation properties of various conformers were evaluated using the Kamlet‐Jacobs equations, and it was found that all the calculated results are comparable to the available experimental data. In addition, the calculated results demonstrate that all title compounds can be used as excellent propellant ingredients. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Präparative und spektroskopische Untersuchungen an einigen substituierten Trisilanen

Zusammenfassung Für Si₃Cl₈ (I) wird eine verbesserte Darstellungsmethode angegeben, Si₃(OCH₃)₈ (II) wird erstmals dargestellt. Die Schwingungsspektren von I, II und Si₃(C₆H₅)₈ werden aufgenommen und unter Berücksichtigung von Kopplungseffekten zugeordnet; insbesondere wird die Lage der beiden SiSi₂-Valenzschwingungen diskutiert.

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Preparative and spectroscopic investigations of some substituted trisilanes

An improved preparation for Si₃Cl₈ and the preparation and properties of the new trisilane Si₃(OCH₃)₈ are described. The vibrational spectra of these compounds and of Si₃(C₆H₅)₈ are reported and assigned, considering vibrational coupling. The position of the two SiSi₂ stretching vibrations is discussed in detail.

     

Vibrational Predissociation Spectra of C2N− and C3N−: Bending and Stretching Vibrations

We present infrared predissociation spectra of C₂N⁻(H₂) and C ₃N⁻(H₂) in the 300–1850 cm⁻¹ range. Measurements were performed using the FELion cryogenic ion trap end user station at the Free Electron Lasers for Infrared eXperiments (FELIX) laboratory. For C₂N⁻(H₂), we detected the CCN bending and CC−N stretching vibrations. For the C₃N⁻(H₂) system, we detected the CCN bending, the CC−CN stretching, and multiple overtones and/or combination bands. The assignment and interpretation of the presented experimental spectra is validated by calculations of anharmonic spectra within the vibrational configuration interaction (VCI) approach, based on potential energy surfaces calculated at explicitly correlated coupled cluster theory (CCSD(T)-F12/cc-pVTZ−F12). The H₂ tag acts as an innocent spectator, not significantly affecting the C_2,3N⁻ bending and stretching mode positions. The recorded infrared predissociation spectra can thus be used as a proxy for the vibrational spectra of the bare anions.     

Syntheses and structures of mononuclear and binuclear transition metal complexes (Cu,Zn, Ni) with (salicylideneglycine and imidazole)

Four transition metal (Cu(II), Zn(II) and Ni(II)) complexes with a Schiff-base ligand (salicylideneglycine) have been synthesized. All complexes have been characterized by elemental analysis, IR spectra and UV-vis spectroscopy. Single-crystal analyses were performed with (C₉H₇NO₃)Cu(C₃H₄N₂) (1), (C₉H₇NO₃)Zn(C₃H₄N₂)₂ (2), (C₉H₇NO₃)₂Ni₂(C₃H₄N₂)₄ (3) and (C₉H₇NO₃)Ni(C₃H₄N₂)₂(C₄H₅N₂O) · CH₃OH · 0.5H₂O (4) and fluorescence spectra and thermogravimetric analyses were also carried out. Structural analyses show that 1, 2 and 4 have similar coordinated modes with the tridentate amino-Schiff-base ligand, but differ from the binuclear nickel complex 3. The tridentate amino-Schiff-base ligand contains aliphatic nitrogen, phenoxy, and carboxylic oxygen as three donor atoms. In addition, inter- and intra-molecular hydrogen bonds are also discussed.     

Synthesis,molecular and electronic structures of half-sandwich ruthenium(II) complexes with pyrimidine-based ligands

The complexes [(C₆H₆)RuCl₂(Hmtp)] and [(C₆H₆)RuCl₂(C₄H₄N₂)] have been prepared and studied by IR, ¹H NMR, UV–VIS spectroscopy and X-ray crystallography. The complexes were prepared by reactions of [(C₆H₆)RuCl₂]₂ with 7-hydroxy-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine (Hmtp) and pyrimidine, respectively, in methanol. The electronic structures and UV–Vis spectra of the complexes have been calculated using the TD–DFT method.     

Untersuchungen an Zinnverbindungen. XVII. Infrarot-, RAMAN-, Mossbauer- und massenspektroskopische Untersuchungen an Triorganozinnfluoriden

The IR, in the solid state (33 to 4000 cm^?1) and in gaseous state, the RAMAN , MÖSSBAUER and mass spectra of (CH₃)₃SnF, (C₂H₅)₃SnF, (n-C₃F₇)₃SnF, (n-C₄H₉)₃SnF and (C₆H₅)₃SnF were recorded. The frequencies of the vibrational spectra were almost completely assigned. By means of this methods the properties of the triorganyl tin fluorides, which differ considerably from the other organyl tin halides, were examined. The difference in their properties are due in all cases to strong intermolecular interactions.     

Mass spectra of monohapto-cyclopentadienyl derivatives of group IVB elements

Dissociative ionisation of organometallic cyclopentadiene derivatives containing one, two or three M(CH₃)₃ groups (M  Si, Ge, Sn) has been studied.Among the monometallated compounds, C₅H₅Si(CH₃)₂Cl, C₅H₅Si(CH₃)₂OCH₃ and (C₅H₅)₄Sb have also been investigated. To verify fragmentation patterns, the spectra of deuterated compounds such as C₅D₅Si(CH₃)₃, C₅D₅Sn(CH₃)₃, C₅D₄Si₂(CH₃)₆ and C₅D₃Si₃)₉ have been measured. Dissociative ionisation of h¹-cyclopentadienyl derivatives has been shown to differ essentially from that of h⁵-compounds.     

Researches by the method of low-temperature adiabatic calorimetry and quantum chemical computation of vibrational states

The temperature dependence of heat capacity of a natural zinc silicate, hemimorphite Zn₄Si₂O₇(OH)₂·H₂O, over the temperature range 5–320 K has been investigated by the method of low-temperature adiabatic calorimetry. On the basis of the experimental data on heat capacity over the whole temperature interval, its thermodynamic functions C _p (T), S(T) and H(T) ? H(0) have been calculated. The existence of a phase transition in the area of 90–105 K determined on the basis of vibrational spectra has been confirmed, and changes of entropy ΔS _tr. and enthalpy ΔH _tr. of the phase transition have been calculated. Hemimorphite heat capacity has also been determined by the calculation methods according to the valence force field model in LADY program. The values of force constants of valence bonds and angles have been calculated by semi-empirical method PM5. The calculated IR and Raman spectra concordant with the experimental spectra have been obtained. The heat capacity values calculated according to the found vibrational states satisfactorily agree with those experimentally obtained with an accuracy of ±1.7% in the area of 120–200 K, and not more than ±0.8% for the interval of 200–300 K. This fact testifies that the calculation of thermodynamic characteristics is correct.     

Sulfenamides as ligands in transition metal chemistry Pentacarbonyl(Sulfenamide)Chromium(0) Complexes

The complexes Cr(CO)₅(R′SNR₂) [R′ = CH₃; NR₂ = N(CH₃)₂, N(C₄H₈)O. R′ = C₆H₅; NR₂ = N(CH₃)₂, N(C₄H₄)O, N(CH₂? C₆H₅)₂, N(C₆H₁₁)₂] have been prepared by reaction of the sulfenamides with Cr(CO)₅ · THF and characterized by analytical and spectroscopic methods. The IR, ¹H-NMR, UV-VIS, and mass spectra of the complexes support the coordination of the sulfenamide via the sulfur atom. π-acceptor abilities of sulfenamides in the prepared coordination compounds, determined from IR and UV-VIS data, were compared with those of other divalent sulfur conpounds.     

Regioselective Sequential Additions of Nucleophiles and Electrophiles to Perfluoroalkylfullerenes: Which Cage C Atoms Are the Most Reactive and Why?

The sequential addition of CN^? or CH₃^? and electrophiles to three perfluoroalkylfullerenes (PFAFs), C_s‐C₇₀(CF₃)₈, C₁‐C₇₀(CF₃)₁₀, and C_s‐p‐C₆₀(CF₃)₂, was carried out to determine the most reactive individual fullerene C atoms (as opposed to the most reactive C?C bonds, which has previously been studied). Each PFAF reacted with CH₃^? or CN^? to generate metastable PFAF(CN)^? or PFAF(CH₃)₂^2? species with high regioselectivity (i.e., one or two predominant isomers). They were treated with electrophiles E⁺ to generate PFAF(CN)(E) or PFAF(CH₃)₂(E)₂ derivatives, also with high regioselectivity (E⁺=CN⁺, CH₃⁺, or H⁺). All of the predominant products, characterized by mass spectrometry and ¹⁹F NMR spectroscopy, are new compounds. Some could be purified by HPLC to give single isomers. Two of them, C₇₀(CF₃)₈(CN)₂ and C₇₀(CF₃)₁₀(CH₃)₂(CN)₂, were characterized by single‐crystal X‐ray diffraction. DFT calculations were used to propose whether a particular reaction is under kinetic or thermodynamic control.