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     

5-羟基嘧啶——Ⅳ.5-烷氧基-5-烷基-2-硫代巴比酸和有关化合物的合成

自烷氧基乙酸乙酯的乙氧草酰化,继以热裂去羰化反应,合成了一系列烷氧基丙二酸二乙酯(Ⅵ,R=n-C₃H₇,n-C₄H₉,iso-C₄H₉,iso-C₅H₁₁和C₆H₅CH₂);进一步烷基化,得到烷氧基烷基丙二酸二乙酯(Ⅶ,R'=CH₃,C₂H₅,n-C₃H₇和n-C₄H-9)。烷氧基烷基丙二酸二乙酯(Ⅶ)与脲、硫脲和与胍的缩合的容易程度相差颇巨。除苯甲氧基乙基丙二酸二乙酯曾与脲缩合生成相应的5,5-二取代巴比酸(I,Y=O)外,其他的各烷氧基烷基丙二酸二乙酯(Ⅶ)均未能与脲顺利地发生缩合。各烷氧基烷基丙二酸二乙酯(Ⅶ)与硫脲的缩合效果较佳,但其中仍有若干未能得到所期望的2-硫代巴比酸(I,Y=S)。两个系列的烷氧基烷基丙二酸二乙酯(Ⅶ,R=n-C₃H₇和C₆H₅CH₂;R'=CH₃,C₂H₅,n-C₃H₇,和n-C₄H₉)与胍的缩合非常顺利,生成相应的5,5-二取代-2-亚氨基巴此酸(I,Y=NH)。5-苯甲氧基-5-烷基-2-亚氨基巴比酸还进行了氢解,得到相应的5-羟基-5-烷基-2-亚氰基巴比酸(I,R=H,R'=烷基,Y=NH)。     

苯胺基桥联双芳氧基稀土金属配合物的合成、表征及催化性能

通过配体前体苯胺基桥联双酚（PhN｛CH₂-（2-HO-C₆H₂-B{\mathrm{u}}_{\mathrm{2}}^t-3,5）｝₂,L¹H₂）与三硅胺基稀土金属配合物的质子交换反应,合成了苯胺基桥联双芳氧基稀土金属配合物,发现反应介质对反应的产物有明显的影响。L¹H₂与Ln［N（TMS）₂］₃（μ-Cl）Li（THF）₃以物质的量比1∶1在甲苯中90 ℃下反应,可以得到预期的苯胺基桥联双芳氧基稀土金属胺化物L¹LnN（TMS）₂（THF） （Ln=Yb（1）,Sm（2））。而L¹H₂与Sm［N（TMS）₂］₃（μ-Cl）Li（THF）₃以1∶1的物质的量比在四氢呋喃（THF）中50 ℃下反应,则得到钐-锂杂双金属配合物（THF）LiL¹₂Sm （3）。这些配合物均经过了红外光谱、元素分析和单晶结构测定的表征。发现配合物1和2可以有效地催化L-丙交酯和D,L-丙交酯的开环聚合,得到高相对分子质量的聚丙交酯。其中,配合物1对D,L-丙交酯的开环聚合显示很好的选择性,可以得到杂同含量（Pr）达到0.87的聚丙交酯。     

新型双苯并环己酮芳亚胺镍(Ⅱ)催化降冰片烯与甲基丙烯酸丁酯共聚合

采用自制的新型双苯并环己酮芳亚胺镍催化剂双苯并环己酮-2,6-二甲基苯亚胺镍(Ⅱ)(Ni{C₁₀H₈(O)C[2,6-C₆H₃(CH₃)₂N]CH₃}₂, C1)和双苯并环己酮-2,6-二氯苯亚胺镍(Ⅱ)(Ni{C₁₀H₈(O)C[2,6-C₆H₃Cl₂N]CH₃}₂, C2)与三五氟苯硼[B(C₆F₅)₃]结合, 在一定的反应条件下可高效催化降冰片烯(NB)与甲基丙烯酸正丁酯(n-BMA)的乙烯基加成共聚合. 提出了催化聚合时存在的可能失活机理; 研究了不同单体投料比对催化活性、 产率及产物性能的影响. 根据Kelen-Tüdõs方法分别估算出2种单体在不同催化体系下的竞聚率, 即当催化体系为C1/B(C₆F₅)₃时, 竞聚率r_n-BMA=0.02, r_NB=16.28, r_NB·r_n-BMA=0.32; 当催化体系为C2/B(C₆F₅)₃时, r_n-BMA=0.01, r_NB=64.83, r_NB·r_n-BMA=0.65. 结果表明, 2种单体在2种体系催化下均为无规共聚合.     

一系列基于杂多酸构筑的配合物的合成,晶体结构及光催化性能

通过引入菲咯啉衍生物配体并改变反应体系中的金属盐,得到了3个新的含有杂多酸的金属-有机配合物（MOCs）,{[Cu₂（Do）₂（H₂O）₄(SiW₁₂O₄₀)]·10H₂O}_n（1）,[Ag₃（Do）₅][Ag（Do）₂](SiW₁₂O₄₀)（2）,[Cu₂（Do）₄（H₂O）₂Cl](PMo₁₂O₄₄)·2CH₃OH（3）（Do=1,10-菲咯啉-5,6-二酮）。在配合物1中,Keggin型杂多酸与Cu（Ⅱ）连接形成了二维网状结构。配合物2中的Ag（Ⅰ）显示了多种不同的配位模式,构建了一个新颖的线性三核簇状结构。在配合物3中,Cu（Ⅱ）通过氯原子连接形成了一个双核结构。结构多样性表明金属离子与第二配体Do在构建不同结构的POMs中起到很重要的作用。光催化研究表明,配合物3不仅能在UV光照射下有效地催化降解罗丹明B（RhB）,而且很稳定,能够从反应体系中分离以循环利用。     

High Temperature Iron Ethylene Polymerization Catalysts Bearing N,N,N'-2-(1-(2,4-Dibenzhydryl-6-fluorophenylimino)ethyl)-6-(1-(arylphenylimino)ethyl)pyridines

The N,N,N’-ferrous chloride complexes,[2-{CMeN(2,4-(CHPh)₂-6-FC₆H₂)}-6-(CMeNAr)C₅H₃N]FeCl₂(Ar=2,6-Me₂C₆H₃ Fe1,2,6-Et₂C₆H₃Fe2,2,6-ⁱPr₂C₆H₃ Fe3,2,4,6-Me₃C₆H₂ Fe4 and 2,6-Et₂-4-MeC₆H₂ Fe5),each possessing one N-2,4-dibenzhydryl-6-fluorophenyl group,were readily...     

硼化合物研究(Ⅲ)——B10H102-、B12H122-以及B3H8-阴离子的二茂铁季铵盐的合成

本文通过B_nH_n^2-(n=10,12)及B₃H₈^-盐分别与C₅H₅FeC₅H₄CH₂N(R)Me₂Cl和Fe(C₅H₄CH₂N(R)Me₂Cl)₂(R=CH₃-,C₂H₅-,n-C₃H₇-,CH₂=CH-CH₂-和CH≡C-CH₂-)在水溶液中进行反应,合成了相应的三十个新的硼烷阴离子衍生物,这些化合物对水稳定性好,B₁₀H₁₀^2-及B₁₂H₁₂^2-衍生物对热、酸、碱和氧化剂均很稳定。研究了反应物之间的用量比例对反应产物的影响。实验结果表明,不论反应物之间的克分子比如何变化,只能得到相应的一种产物(产率90-98％)。     

酚羟基席夫碱钯配合物的合成、表征及其催化性能

以Na₂PdCl₄与(2-NC₅H₄)C(H)=N(C₆H₄OH-2)在不同溶剂中合成了两个钯配合物 Pd{2-(NC₅H₄)C(H)=N[2-（OH）C₆H₄]}Cl₂（Complexe 1）和 Pd{2-(NC₅H₄)C(H)=N[2-(O)C₆H₄]}Cl（Complexe 2）。X射线单晶衍射确定了配合物的分子结构,在配合物1和2中,氯离子的配位个数对所形成的配合物的四边形结构产生一定的影响。两种钯配合物的催化活性通过空气中在醇溶剂体系下4-碘甲苯和苯硼酸的Suzuki-Miyaura反应进行评价。结果显示：催化产物4-甲基联苯的产率可达98.72%和92.31%,副产物联苯的产率小于1.15%,进一步通过配合物的单晶结构数据分析了不同配位模式对催化活性的影响。      

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.     

Synthesis, characterization of neodymium chloride complex of amine-bis(phenolate) ligand and its reactivity in the ring-opening polymerization of ε-caprolactone

The neodymium chloride complex[Nd（ONN’O）Cl（THF）]₂ supported by amine-bis（phenolate） ligand was synthesized by the metathesis reaction of anhydrous NdCl₃ with Li₂（ONN’O）[H₂ONN’O = Me₂NCH₂CH₂N（CH₂-3-Bu₂^t-5-Me-C₆H₂OH）₂]in high yield.X-ray structural determination shows[Nd（ONN’O）Cl（THF）]₂ complex consists of two seven-coordinate neodymium centers linked throughμ-Cl bridges.And this complex was successfully used to initiate the ring-opening polymerization（ROP） ofε-caprolactone.     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

In this work, ferrocene- and ferrocenium-containing salts were employed to modify montmorillonite. X-ray measurements show an increase in the interlayer spacing upon clay modification, which means that the larger and more organophilic cations were inserted into the gallery space of montmorillonite. Attempts to prepare nanocomposites of polystyrene and ethylene vinyl acetate copolymers lead to immiscible systems; the morphology of these systems was elucidated with TEM, XRD and cone calorimetry. The thermal stability of the composites is greater than that of the virgin polymer.     

Synthesis and Optical and Redox Properties of Symmetric and Asymmetric BODIPYs

Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red‐emitting boron‐dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single‐ and double‐substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non‐radiative deactivation processes can be softened by decreasing the electron‐donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red‐edge BODIPYs with highly efficient and photostable laser emission.     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.     

含茂基苯并三氮唑基镧系有机配合物的合成及表征

三茂基镧系化合物和苯并三氮唑在四氢呋喃中反应,合成了7个未见文献报道的含茂基苯并三氮唑基镧系有机配合物,经元素分析、IR和MS测定,从有关数据推测了这类配合物的可能结构。     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。