[Mo2O2S2(S2)2][2-]的振动光谱研究

本文测定了原子簇化合物[Mo2O2S2(S2)2][2-]的红外和拉曼光谱,并在乙腈溶液中测得其共振拉曼光谱和退偏振比。利用X光晶体结构数据,对此阴离子的伸缩振动作了简化的正则坐标分析计算。所得结果可以帮助分析和归属一些Mo-Fe-S原子簇化合物的振动光谱。     

2MgO·2B2O3·MgCl2·14H2O-MgCl2-H2O体系30℃相平衡

用相平衡方法研究2MgO@2B2O3@MgCl2@14H2O在30℃不同质量分数MgCl2水溶液中的溶解转化产物及其溶解度.结果表明,该复盐在MgCl2的质量分数0～2%浓度范围,发生不同步溶解并转化为多水硼镁石(2MgO@3B2O3@15H2O);在MgCl2的质量分数2%～13.8%浓度范围,转化为柱硼镁石(MgO@B2O3@3H2O),这一结果比文献报导的该硼酸盐的形成温度低了13℃,为盐湖硼酸镁矿物柱硼镁石形成的解释提供了物理化学依据;而在MgCl2质量分数大于13.8%时,同步溶解,不发生转化.提出了溶解相转化反应机理.     

Na2WO4·2H2O-H2O2催化氧化苯甲醛制备苯甲酸

以30%H2O2为氧源,Na2WO4·2H2O催化氧化苯甲醛制备苯甲酸.考察了H2O2用量,反应时间,催化剂和酸性添加物(硫酸氢钠)对苯甲酸收率的影响和在非酸性环境下,表面活性剂对苯甲酸收率的影响.结果表明,加入非离子表面活性剂能有效的提高苯甲酸的收率,特别是添加β-环糊精,苯甲酸的收率达90.03%.     

PdC_2H_2和PtC_2H_2的键结构研究

关于过渡金属Pd,Pt对C_2H_2的吸附和氢化实验研究前人已作了不少工作,但有关Pd,Pt与C_2H_2之间成键问题的理论研究还尚不多见。为了了解Pd,Pt d轨道对炔键的活化行为和成键特性,本文以MC_2H_2(M=Pd,Pt)为模型,用赝势计算方法,对Pd,Pt与C_2H_2键的相互作用进行了研究。一、计算方法由于重原子的内层轨道对形成分子贡献很小,内层电子的相对论效应极为严重。本文采用Ps—HONDO程序,选取Hay的有效核芯势和价轨道Gaussian基组,对重原子Pd和Pt进行了价电子从头计算,对C和H进行了全电子从头算.部分地消除重原子内层电子相对论效应所引起的误差。     

Cl_2 2HI=2HCl I_2反应机理的理论研究

分别在MP2/3-21G!!、CCSD(T)/3-21G!!//MP2/3-21G!!和B3LYP/3-21G!!3种水平上,计算研究了气相反应Cl2 2HI=2HCl I2的机理,求得一系列四中心和三中心的过渡态.通过比较六种反应通道的活化能大小,得到了相同的结论:双分子基元反应Cl2 HI"HCl ICl和ICl HI"I2 HCl的最小活化能小于Cl2、HI和ICl的解离能,从理论上证明了反应Cl2 2HI=2HCl I2将优先以分子与分子作用形式分两步完成.用内禀反应坐标(IRC)验证了MP2/3-21G!!方法计算得到的过渡态.     

O2 和 CO 在 Co2B2/TiO2 和 Co2B2Pt/TiO2 表面吸附的密度泛函研究

 采用密度泛函理论探讨了 TiO2 表面负载 Co2B2 和 Co2B2Pt 合金簇可能的负载构型. 结果表明, Co2B2 和 Co2B2Pt 合金簇倾向于以两个 Co 的形式负载在两个氧上. 态密度分析发现, 负载后, Co2B2 合金簇中部分 Co 原子和 B 原子成键加强, Co2B2Pt 合金簇中 Pt 原子和 B 原子成键也加强, 形成新的轨道. CO 和 O2 在 Co2B2/TiO2 和 Co2B2Pt/TiO2 表面吸附的结果表明, Co2B2Pt/TiO2 催化氧化 CO 性能的提高是由于 Pt 原子提高了 Co2B2 合金簇吸附 CO 和 O2 的能力.     

五元体系K2+2,Mg2+∥Cl2-2,SO2-4-CO(NH2)2-H2O及其边界四元体系MgSO4-MgCl2-CO(NH2)2-H2O在25 ℃时的等温溶度研究

报道了五元体系K2+2, Mg2+∥Cl2-2,SO2-4-CO(NH2)2-H2O在脲不饱和区及其边界四元体系MgSO4-MgCl2-CO(NH2)2-H2O在25 ℃时的等温溶度研究结果, 绘制了体系等温溶度的盐分组成图、水量图以及饱和溶液的折光率-组成图. 五元体系在脲的参与下, 交互反应K2Cl2+MgSO4→K2SO4+MgCl2向有利于生成硫酸钾和软钾镁矾K2SO4*MgSO4*6H2O(pic.)的方向进行, 这两者的相区较无脲时明显增大.     

Na2O2与NO2不反应吗

通过实验验证,指出了一些期刊涉及Na2O2吸收CO2和NO混合气体的规律性等文章的知识性错误,认为习题训练中应回避此类问题,或是以此问题对学生置疑,引导学生实验探究,进行批判性教学。     

二聚体有机锡配合物{[n-Bu2SnO2CCH(CS2NEt2)2]2O}2的合成、表征及晶体结构

近年来,有机锡(Ⅳ)的羧酸配合物因其具有很强的生物活性以及丰富的结构类型备受人们的重视．实验证明,它们的生物活性与锡原子的配位形式有关,而中心锡原子的配位形式决定于直接与锡原子相连的烃基的结构和羧酸基配体的类型。     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.     

Formal [(2+2)+2] and [(2+2)+(2+2)] nonconjugated dienediyne cascade cycloadditions

[reaction: see text] Fluoranthene 2 and heptacycle 3 are easily accessible from the reaction of diyne 1 and norbornadiene (NBD) in the presence of the rhodium catalyst. The unusual [(2+2)+(2+2)] adduct 3 was confirmed by the X-ray crystal structure analysis.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Die Photoionenspektren von SCl2, S2Cl2 und S2Br2

Photoionization Mass Spectra of SCl₂, S₂Cl₂, and S₂Br₂ Photoionization mass spectra of SCl₂, S₂Cl₂, and S₂Br₂ have been measured. Heats of formation, bond energies, and ionization potentials of fragments have been calculated from appearance potentials.