Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

Ternary surface complexes by theE(%)-pH curve method

A new method for the study of ternary surface complexes at liquid-solid interface, theE(%) -pH curve method, was proposed. Four types ofE(%)-pH curves, namely, phenomenon of left-right shifts of S-shaped curve, V-shaped curve, monodirection shift curve and X-shaped curve, were discovered. Correspondingly, apart from type (I) ternary surface complex and type (II) ternary surface complex , a new type of ternary surface complex was discovered. Project supported by the National Natural Science Foundation of China and the Fund of Doctoral Degree’s Spot.     

Residence times in kink sites and Markov chain model of alloy and intermetallic compound deposition

The concept of the residence time τ_ksp of an atom in a kink site has recently been suggested to understand the processes in electrochemical deposition of alloys and intermetallic compounds. Different kink sites with different residence times must be defined for alloys and intermetallic compounds. Based on this model, the finite Markov chain theory is applied to describe the selectivity of the growth process. An analytical relationship between the alloy composition and the metal ion concentrations in the electrolyte is derived. General model parameters are ratios g _i = K _ii/K _ij of equilibrium constants of the reaction of electrolyte ions with different kink sites on the surface (i, j representing different alloy components). These ratios are called selectivity constants. For simple conditions, the equation g _i ≈ τ_ii/τ_ij connects the g _i values with the residence times. The theory is tested in the deposition of alloys Co-Ni (anomalous co-deposition) and Ni-Mo (induced co-deposition). Additionally, Bi₂Te₃, an example of stoichiometric semiconductor deposition, is treated. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1216–1223. The text was submitted by the authors in English.     

桥联双β-环糊精对N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸的手性识别及机理研究

利用紫外-可见吸收和荧光发射光谱, 结合非线性最小二乘法拟合曲线以及分子力学(MM2)模拟系统地研究了手性分子N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸(PDP和PLP, 总称PPs)与β-环糊精(β-CD)、 2-位硒桥联双β-CD(2-SeCD)和2-位碲桥联双β-CD(2-TeCD)的包结能力大小及这3个环糊精对PPs手性识别能力的差异和识别机理. 研究结果表明, PPs不能与单疏水空腔的β-CD形成很好的包结复合物, 与具有较长桥联链的2-TeCD结合能力最强. 2-TeCD与PDP和PLP的结合常数分别为2.33×104和6.07×103 L/mol, 对PPs的手性识别比达到KD/KL=3.84, 高于2-SeCD(KD/KL=2.61). 用MM2模拟得出了PPs与这两个双环糊精形成复合物的三维结构: PPs的绝大部分位于双环糊精两个空腔之间, 但是在这两个复合物中, 苯环与芘环所成的二面角不同. 此外, PPs与这两个双环糊精作用时均存在明显的氢键相互作用, 且2-TeCD强于2-SeCD.     

计算金属间化合物热力学性质的新方法

用一简单的相关函数式对金属间化合物的热力学性质进行拟合，提出了一种计算金属间化合物热力学性质的新方法，并用此方法计算了二元金属间化合物的常温热容和熵。计算结果表明，该方法简单，且能满足一定的计算精度，有一定的实用价值。     

膦取代的羰基铂簇的合成,结构和性质

Pt(PPh_3)_2Cl_2在碱性介质中,与一氧化碳直接进行还原及羰基化反应,得到五种膦取代的羰基铂配合物:Pt_5(μ_2-CO)_5(CO)(PPh_3)_4 1,Pt_3(μ_2-CO)_3(PPh_3)_3 2,Pt_3(μ_2-CO)_3(PPh_3)_4 3,Pt_4(μ_2-CO)_5(PPh_3)_4 4,以及Pt(Cl)(PPh_3)_2(COOCH_3) 5。经X-射线单晶衍射分析,确定了新的三核铂羰基簇2以及配合物5的分子结构。还讨论了1和5的生成机理。     

Joule-Thomson inversion curve prediction by using equation of state

In this paper five equations of state are tested for checking their ability to predict the Joule-Thomson inversion curve.These five equations of state are:Mohsennia-Modarres-Mansoori(MMM),Ji-Lemp(JL),modified Soave-Redlich-Kwang(SRK)equation of state by Graboski(MSRK1),modified SRK equation of state by Peneloux and Rauzy(MSRK2),and modified Peng-Robinson (PR)equation of state by Rauzy(PRmr).The investigated equations of state give good prediction of the low-temperature branch of the inversion curve,except for MMM equation of state.The high-temperature branch and the peak of the inversion curve have been observed,in general,to be sensitive to the applied equation of state.The values of the maximum inversion temperature and maximum inversion pressure are calculated for each component used in this work.     

Preparation of cellulose and cellulose derivative azo compounds

Wood pulp and cotton linter are the most common sources of cellulose forindustrial use. Methyl cellulose (MC) and cellulose sulfate (CS) were preparedusing bleached wood pulp and cotton linter. Coloured azo compounds were alsoprepared from coupling cellulose, wood pulp, MC and CS with aromatic diazoniumsalt. The presence of electron-releasing or withdrawing substituents affectedthe electrophilic substitution reaction. The produced azo compounds werecharacterized by FT-IR methodology, as well as mass spectrometry, in which thefunctional groups and the ion fragments of the products were analyzed.     

以钛氧有机物为前驱物制备具有高光催化活性的纳米二氧化钛晶体

 纳米二氧化钛的制备方法及前驱物的差别影响其光催化活性．将20ml钛酸丁酯及30ml乙酐在密闭容器中与50ml环己烷混合，在70～85℃反应30min，生成微细的非晶钛氧有机物；经FT－IR和TGA分析，该物质被确认为计量式是TiOOOCCH3）2和TiO（OC4H9）（OOCCH3）的混合体．该钛氧有机物前驱物经焙烧后得到具有高光催化活性的纳米二氧化钛晶体．表征结果表明，钛氧有机物在焙烧过程中，其表面的吸附物及键合有机基团在400℃以前发生脱附和氧化分解；在389～405℃间形成锐钛矿型晶体，在600℃出现金红石晶型；600℃焙烧3h所得样品的比表面积为86m2／g，其二次粒子呈200～300nm条形体，孔隙大于20nm；单分散粒子为球形单晶，粒径为22nm；表面物理吸附水量为1．21％，加热至800℃时失重1．48％，粉体稳定纯净．光催化实验结果表明，以钛氧有机物为前驱物制备的纳米二氧化钛晶体具有高的光催化活性，光降解丁基罗丹明溶液的反应速率常数约为溶胶－凝胶法制备的催化剂样品的4倍．表面氧空缺和一定量的表面羟基可能是粉体具有高光催化活性的重要因素．     

Syntheses, crystal structures and magnetic properties of a new nitronyl nitroxide NIT2-bithph and its manganese(II) compound [Mn(hfac)2(IMHBithph)]2·(NIT2-bithph)(C6H14)

A new nitronyl nitroxide NIT2-bithph (1) and its manganese(II) compound [Mn(hfac)₂(IMHBithph)]₂·(NIT2-bithph)(C₆H₁₄) (2) (hfac = hexafluoroacetylacetonate; NIT2-bithph = 4,4,5,5-tetramethyl-2-(bithiophenal-2-yl)imidazoline-1-oxyl-3-oxide; IMHBithph = 1-hydroxy-2-bithiophenal-4,4,5,5-tetramethyl-4,5-dihydro- 1H-imidazole) have been synthesized and structurally characterized by X-ray diffraction methods. The units of compound 1 were connected as one-dimensional chain by the intermolecular hydrogen bonds which afford an intermolecular antiferromagnetic interaction between nitronyl nitroxide radicals within the chain (J = −1.89 cm⁻¹). Compound 2 resulting from the reaction of Mn(hfac)₂·2H₂O and NIT2-bithph is dinuclear and includes the reduced amidino-oxide form of NIT2-bithph, it is made up of three parts: a [Mn(hfac)₂(IMHBithph)]₂ dimer unit, an uncoordinated NIT2-bithph radical and a noncoordinated solvent molecule of hexane, the molecule of radical is hydrogen bonded to its reduced form. Two reduced IMHBithph ligands bridge the two manganese(II) ions through their amidino-oxide oxygen atoms resulting in a small intramolecular antiferromagnetic interaction between the manganese ions (J = −1.55 cm⁻¹).