吡啶－2，6－二甲酸镧钇异核配合物的合成及晶体结构

合成了吡啶－２，６－二甲酸镧钇异核配合物晶体。元素分析结果表明，化学式为ＬａＹ（ＨＤＰＡ）＿２·（ＤＰＡ）＿２．１２Ｈ＿２Ｏ，ＤＰＡ为吡啶－２，６－二甲酸根。用Ｘ射线衍射法测定了配合物的单晶结构，其结构式为［ＬａＹ（ＨＤＰＡ）＿２（ＤＰＡ）＿２（Ｈ＿２Ｏ）＿４」·８Ｈ＿２Ｏ，属单斜晶系，Ｐ２＿１／ａ空间群。晶胞参数：ａ＝１．２９７５（４）ｎｍ，ｂ＝１．１２６６（３）ｎｍ，ｃ＝１．４０７９（３）ｎｍ；β＝１０２；１５（２）°，Ｖ＝２．０１１９０（１）ｎｍ￣３，Ｚ＝４，Ｄｃ＝１．８３ｇ／ｃｍ￣３，稀土离子的配位数为９，其配位多面体为扭曲的三冠三角棱柱体。

ELECTROCHEMICAL DETECTION OF COBALT IN HAIR FOLLOWING ON-COLUMN DERIVATIZATION WITH 1-(2-PYRIDYLAZO)-2-NAPHTHOL-6-SULFONIC ACID AND REVERSED-PHASE LIQUID-CHROMATOGRAPHY

A method for the specific determination of cobalt based on reversed-phase liquid chromatography with amperometric detection via on-column complex formation has been developed. A water-soluble chelating agent, 1-(2-pyridylazo)-2-naphthol-6-sulphonic acid (PAN-6S), is added to the mobile phase and aqueous cobalt solutions are injected directly into the column to form in situ the cobalt-PAN-6S chelate, which is then separated from other metal PAN-6S chelates and subjected to reductive amperometric detection at a moderate potential of -0.3 V. Because the procedure eliminates the interference of oxygen and depresses the electrochemical reduction of the mobile phase-containing ligand PAN-6S, by virtue of the quasi:reversible electrode process of the cobalt-PAN-6S complex, a low detection limit of 0.06 ng can be readily obtained. Interference effects were examined for sixteen common metal species, and at a 5- to 8000-fold excess by mass no obvious interference was observed. The feasibility of the method as an approach to the specific analysis of cobalt in a hair sample has been demonstrated.

THE CLEAVAGE REACTION OF THE MO-MO TRIPLE BOND - THE CRYSTAL-STRUCTURES OF MOLYBDENUM COMPLEXES [CPMO(CO)(2)(C(5)H(4)NS)], [CPMO(CO)(2)(C(9)H(6)NS)]O=PPH(3) AND [CPMO(CO)(2)(S(2)CNME(2)]

The reactions of [Cp2Mo2(CO)4] (1) with 2,2'-dipyridyl disulphide (C5H4NS-)2, 8,8'-diquinolyl disulphide (C9H6NS-)2 and tetramethyl thiuram disulphide (Me2NC(S)S-)2 in toluene solution resulted in the cleavage of the Mo-Mo triple bond to yield molybdenum complexes [CpMo(CO)2(C5H4NS)] (2), [CpMo(CO)2(C9H6NS)] (3) and [CpMo(CO)2(S2CNMe2)] (4), respectively. The molecular structures of 2, 3 . O=PPh3 and 4 were determined by X-ray diffraction studies. Crystals of 2 are monoclinic, space group P2(1)/n, with Z = 4, in a unit cell of dimensions a = 6.448(1), b = 12.616(2), c = 14.772(2) angstrom, beta = 92.85(1)-degrees. The structure was refined to R = 0.028 and R(w) = 0.039 for 1357 observed reflections. Crystals of 3 . O=PPh3 are triclinic, space group P1BAR, with Z = 2, in a unit cell of dimensions a = 11.351(3), b = 13.409(3), c = 9.895(2) angstrom, alpha = 94.59(2), beta = 90.35(2), gamma = 78.07(2)-degrees. The structure was refined to R = 0.033 and R(w) = 0.037 for 3260 observed reflections. Crystals of 4 are monoclinic, space group P2(1)/a and Z = 4 with a = 12.468(5), b = 7.637(2), c = 13.135(4) angstrom, beta = 96.62(3). The structure was refined to R = 0.032 and R(w) = 0.042 for 1698 observed reflections. Each of complexes 2-4 contains a cyclopentadienyl ligand, a cis pair of carbonyls and a chelate ligand (S,N donor or S,S donor). All the compounds have distorted square-pyramid structures.

STUDIES ON THE REACTIONS OF TRANSITION-METAL HYDRIDES WITH HETEROCUMULENES .6. REACTION OF CP2ZR(H)CL WITH RNCS (R=C6H5, 2-C10H7, C-C6H11 AND N-C4H9)

The novel NS-containing zirconacycle complexes Cp2ZrCl[SC(H)NR] (1a, R = C6H5; 1b, R = 2-C10H7; 1c, R= C-C6H11; 1d; R = n-C4H9) were obtained by insertion reactions of Cp2Zr(H)Cl with RNCS. 1(a-d) could react further with Cp2Zr(H)Cl to yield a sulphur-bridging compleX (Cp2ZrCl)2S (2) and a Schiff base RN=CH2. The crystal structure of la has been determined by X-ray analysis.

(η~6-Arene)Nd(AlCl_4)_3AIR_3催化丁二烯的聚合

关于η~6-芳烃过渡金属有机络合物催化烯烃聚合的研究已早有报道.但对于η~6-芳烃稀土络合物催化烯烃聚合的研究至今未见报道.我们在研究了(η~6-C_6H_6)Nd-(AlCl_4)_3-AlR_3催化异成二烯聚合的基础上,又考察了不同芳烃烯土络合物和几种AlR_3组成的催化剂对丁二烯聚合的催化活性. 1.原料及试剂:丁二烯和烷基铝均为聚合级.汽油分别经浓硫酸,氢氧化钠水溶

Sm~(3+)在玻璃中的发光以及Sb~(6+)、Ce~(6+)、Gd~(3+)对Sm~(3+)发光性质的影响

本文研究了单掺(Sm~(3+),Ce~(3+)、Gd~(3+).Sb~(3+)、双掺(Sm~(3+)+Ce~(3+)、Sm~(3+)+Gd~(3+),Sm~(3+)+Sb~(3+))和兰掺(Sm~(3+)+Gd~(3+)+Ce~(3+))约四十余种不同玻璃的发射谱和激发谱.探讨了玻璃成份和掺杂离子浓度对Sm~(3+)发光性质的影响以及Ce~(3+),Gd~(3+)、Sb~(3+)、Ce~(3+)+Gd~(3+)对Sm~(3+)的敏化作用。

双环己基18冠6对水/硝基苯界面离子的促进传输

Li~-和H~-因较强的亲水性,较难穿越液/液界面进行传输。本文报道了冠醚双环已基18冠6对Li~+,Na~+,Rb~-和H~-在水/硝基苯界面的促进传输行为,求得了相应促进传输过程的一系列参数,并对被传输离子在传输过程中的形态变化进行了初步的探讨。

A HIGH-RESOLUTION SOLID-STATE NMR-STUDY OF THE MISCIBILITY, MORPHOLOGY, AND TOUGHENING MECHANISM OF POLYSTYRENE WITH POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

An extended Goldman-Shen pulse sequence was used to observe indirectly the proton spin diffusion in the blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxides) (PPO). The results indicate that the average distance between PS and PPO is less than 5 angstrom in the intimately mixed phase, but there are heterogeneous domains on a 100-angstrom scale. The data of spin relaxation of carbons, T1(C), for homopolymers and their blends suggest that there is a strong pi-pi electron conjugation interaction between the aromatic rings of PS and those of PPO, while the aromatic rings of PPO drive the aromatic rings of PS to move cooperatively. It is the cooperative motion that markedly improves the impact strength of PS.

SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF [EU(ETA-6-C6ME6)(ALCL4)2]4 - THE 1ST CYCLOTETRAMERIC LANTHANIDE(II) COMPLEX WITH A NEUTRAL PI-LIGAND

The reaction of EuCl3, AlCl3 and C6Me6 in toluene gives the Eu(II) complex [Eu(eta-6-C6Me6)(AlCl4)2]4; X-ray crystal determination shows the molecule to be a cyclotetramer, in which the four Eu(C6Me6)AlCl4 units are connected via four groups of eta-2-AlCl4.

尼龙6,6(PA_(6,6)及其共混物结晶性能的研究

尼龙6,6(PA_(6,6))是一种典型的结晶性工程塑料,被广泛应用于纺织、机械制造等行业,但其加工温度范围较窄,耐热性差。聚醚砜(PES)具有较高的玻璃化转变温度,是非晶聚合物,可以诱发某些结晶聚合物结晶。PES与PA_(6,6)共混体系的研究报道较少,本文用熔融法将PES与PA_(6,6)制成共混物,企图改善PA_(6,6)的结晶性,以提高其耐热性,取得了较理想的结果。

WATER-SOLUBLE AND AMPHIPHILIC POLYMERS .6. A STUDY ON THE SURFACE-COMPOSITION OF CAST FILMS OF PST/PMAA AND PEO-PST-PEO BLOCK POLYMERS BY XPS

Thin films of PSt/PMAA and PEO-PSt-PEO block polymers were deposited on a polystyrene substrate by solution adsorption (with or without solvent treatment), and the film surfaces were characterized by means of XPS. Direct solvent - casting of PEO-PSt-PEO from benzene solutions resulted in PSt-rich surfaces, whereas PMAA richer surfaces were obtained for PSt/PMAA films cast from DMF solutions. Moreover, solvent treatment after casting had profound effect on the film surface composition. Treatment with water markedly increased the surface concentration of polar PEO segments. In the case of PSt-PMAA block polymers, the PSt content on the surface increased in the order of water < ethanol < cyclohexane < petroleum ether, the last-named giving films with almost pure PSt surface. It is well worth noticing that the bulk composition had little to do with the surface composition for both PSt/PMAA and PEO-PSt-PEO block polymers within the composition range investigated when subsequent solvent treatment was applied.

COMPATIBILIZING EFFECT OF POLY(ETHYLENE OXIDE)-B-POLYSTYRENE-B-POLY(ETHYLENE OXIDE) IN PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

The morphology and mechanical behaviour of phenolphthalein poly(ether ether ketone) (PEK-C)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) blends has been investigated. A poly(ethylene oxide)-b-polystyrene-b-poly(ethylene oxide) (PEO-PS-PEO) triblock copolymer was used as compatibilizer. It was found that PEO-PS-PEO has a compatibilizing effect on the PEK-C/PPO blends. The addition of PEO-PS-PEO to the blends greatly improves phase dispersion and interfacial interfacial adhesion and also enhances the ultimate tensile strength and Young's modulus at compositions ranging from 30 to 70% PEK-C. However, all the values of the ultimate tensile strength within the whole composition range are lower than those expected by simple additivity, probably owing to the poor mechanical properties of PEO-PS-PEO copolymer.

η~6—芳烃希土有机配合物的合成、结构及性能研究——Ⅰ.Sm(η~6—C_6H_6)(AlCl_4)_3的合成及晶体结构

经过铝粉加热活化的AlCl_3与SmCl_3在苯中反应,得到了Sm(η~6—C_6H_6)(AlCl_4)_3·C_6H_6单晶.其晶体属于三斜晶系,P1空间群,晶胞参数a=9.456(2)(?),b=9.765(3)(?),c=16.776(4)(?),α=96.00(2)°,β=93.76(2)°,γ=111.66(2)°,V=1422.55(?)~3,Z=2.晶体结构是采用Patterson和Fourier合成法解出的,所有非氢原子的坐标及各向异性热振动参数经块矩阵最小二乘法修正,最后偏离因子R=0.031,R_ω=0.035.分子结构中,中心离子Sm(Ⅲ)与六个Cl原子及一个苯环上的六个C原子成键.Sm-C键平均距离2.92(?),Sm-Cl平均距离2.83(?).与希土相连的六个Cl原子,其中之五构成平面五边形,整个分子呈大致的五角双锥形.