Synthesis and structures of the complexes of beta-alkoxycarbonylethyltin trichlorides with N-aryl-2-hydroxyacetophenylideneimines

Sixteen novel beta-alkoxycarbonylethyltin trichlorides and the corresponding N-aryl-2-hydroxyacetophenylideneimines complexes have been synthesized and characterized. An X-ray crystal structure analysis of the complex of beta-methyloxycarbonylethyltin trichloride and N-4-methylphenyl-2-hydroxyacetophenylideneimine has been performed, The crystal belongs to space group , The cell parameters are: a = 1.0201(6) nm, b = 1.082 2(4) nm, c = 1.394 9(6) nm, alpha = 99.88(3)degrees, beta = 98.63(4)degrees, gamma = 97.86(4)degrees, Z = 2, The ligands coordinate to tin atom via phenolic oxygen atom. Coordination of carbonyl oxygen atom to tin atom still exists in the complexes, The coordination number of tin atom is 6.

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF THE DAWSON-TYPE TUNGSTOPHOSPHATE HETEROPOLY COMPLEXES SUBSTITUTED BY NIOBIUM

Eight new complexes alpha(2)-M(7-m)H(m)[P2W17NbO62]. H2O and alpha-1, 2, 3-M(g-m)H(m) [P2W15Nb3O62]. XH(2)O(M=K, TMA, TEA, TBA) were synthesized and characterized by IR and UV spectroscopy, polarography, XPS and XRD methods. P-31 and W-183 NMR studies show that the niobium atoms in the anions are on the polar sites. The crystal of alpha-1, 2, 3-K7H2 [P2W15Nb3O62]. 30H(2)O is hexagonal, its cell parameters: a=1.9836(4), b=1.9836(9), c=1.5498(6)nm, alpha=beta=90 degrees, gamma=120 degrees.

STEREOCHEMICAL CONTROL IN PROPYLENE POLYMERIZATION WITH A ASYMMETRICALLY SUBSTITUTED TITANOCENE/METHYLALUMINOXANE CATALYST

A new mono-substituted titanocene, (eta(5)-cyclopentadienyl) [eta(5)-(1-(4-methoxyphenyl) cyclohexyl) cyclopentadienyl] dichlorotitanium (I), has been prepared via a novel modified synthesis, and its X-ray crystal structure has been determined. It crystallizes in the orthorhombic space group P2(1)2(1)2(1) with cell constants a=0.968 0(5) nm, b=1.284 6(5) nm, c=1.694 4(6) nm, Z=4, R=0.066. The I/methylaluminoxane (MAO) catalyst system produces at different polymerization temperatures either an isotactic or a syndiotactic polypropylene, both of which have the combined influence of enantiomorphic-site control and chain-end control, or an atactic polypropylene controlled by Bernoullian propagation mechanism.

铌取代Dawson结构钨磷杂多配合物的合成及其结构表征

本文报道了八种新化合物α_2-M_(7-m)H_m[P_2W_(17)NbO_(62)]·xH_2O,α-1,2,3-M_(9-m)H_m[P_2W_(15)Nb_3O_(62)]·xH_2O(M=K,TMA,TEA,TBA)的合成和表征.红外和紫外光谱表明两种阴离子具有Dawson结构,~(31)P和~(183)W NMR测定结果表明铌原子确系“极位”一、三取代.α-1,2,3-K_7H_2[P_2W_(15)Nb_3O_(62)]·30H_2O为六方晶系,晶胞参数为:a=1.9836(4),b=1.9836(9),C=1.5498(6)nm,a=β=90°,γ=120°.此外,还报道了极谱、XPS和XRD结果.

不对称取代钛茂/甲基铝氧烷催化体系丙烯聚合立构控制

利用一种新合成途径制备了单取代钛茂化合物(η~5-环戊二烯)[η~5-(1-(4-甲氧基苯基)环已烯基)环戊二烯]二氯化钛(Ⅰ),以衍射法确定其晶体结构属正交晶系,空间群P2_12_12_1,晶胞参数a=0.9680(5)nm,b=1.2846(5)nm,c=1.6944(6)nm,Z=4,R=0.066.详尽考察了不同聚合温度条件下Ⅰ/甲基铝氧烷(MAO)催化体系对丙烯聚合的立体化学控制,发现随着聚合温度的变化,能够生成等规、无规、间规三种不同立构取向的聚丙烯;其中等规、间规聚丙烯是由对映结构活性中心及链末端共同控制生成,而无规聚丙烯则受Bernoullian生成方式控制.

轻稀土配合物[Li·(DME)_3ⅡCH_3C_5H_4Ln(NPh_2)_3l(Ln=La、Pr、Nd)的合成和镧配合物的晶体结构

CH_3C_5H_4LnCl_2·2LiCl·nTHF与2mol的LiNPh_2在THF、已烷和甲苯混合液中反应,经DME萃取,得到[Li·(DME)_3][(η~5-CH_3C_5H_4)Ln(NPh_2)_3](Ln=La,Pr,Nd)。对其进行了元素分析、IR和NMR表征。镧配合物单晶结构测定表明,属单斜晶系,P2_1/a空间群,晶胞参数为α=1.7461(6)nm,b=1.6576(5)nm,c=1.8335(6)nm,β=96.04°,V=5.277um~3,Z=4,D_c=1.26g/cm_3,R=0.057,R_w=0.048。该配合物是一个离子对,La-N和La-C(环)键的平均距离分别为0.2459(8)和 0.2843(11)nm。稀土离子形成一个六配位的扭曲四面体。

四甲基乙撑桥联二环戊二烯基环戊二烯基稀土配合物的合成与表征

合成了四个甲基乙撑桥联二环戊二烯基环戊二烯基稀土四氢呋喃配合物,采用元素分析、红外光谱、核磁共板、热失重和质谱等方法对所得到配合物进行表征,并用X光衍射法测得Me_4C_2(C_5H_4)_2SmC_5H_3(THF)的晶体结构。该晶体属正交晶系C_(e2a)空间群,a=1.1696(6),b=1.2539(5),c=2.9432(15)nm;V=4.316(4)nm~3,z=8,D_c=1.54g·cm~(-3)。三个环戊二烯基Sm-C(η~5)距离分别为0.272(3),0.276(3),0.278(3)nm和Sm-O键长为0.253(1)nm。

氯化镱与α-脯氨酸配合物的合成及结构研究

在水溶液中合成了氯化镱与α-脯氨酸(Pro)的配合物,研究了配合物的红外光谱。X射线衍射测定结果表明,其结构式为{[Yb(Pro)_2(H_2O)]Cl_3}_n,属单斜晶系,空间群P_(21),晶胞参数为:a=0.8268(1)nm,b=1.0980(3)nm,c=1.1965(4)nm,β=106.97(2)°,V=1.04120(5)nm~3,Z=2。每两个镱原子之间通过一个脯氨酸的羧基桥相连而形成一维链式聚合物,另一脯氨酸羧基以单齿形式与镱原子配位。镱的配位数为8,配位多面体为三角十二面体。

STUDIES ON ORGANOLANTHANIDE COMPLEXES .40. SYNTHESIS AND X-RAY STRUCTURE OF BIS (2-METHOXYETHYLCYCLOPENTADIENYL) YTTRIUM AND YTTERBIUM TETRAHYDROBORATES

New bis (2-methoxyethylcyclopentadienyl) yttrium and ytterbium tetrahydroborates (Ln = Y, 1; Yb, 2) have been synthesized in good yield by the reaction of bis (2-methoxyethylcyclopentadienyl) lanthanide chlorides (Ln = Y, Yb) with sodium borohydride in THF at room temperature. The title complexes were characterized by elemental analyses, MS, H-1 NMR and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. 1 crystallizes from THF-n-Hexane in space group Pna2(1) with unit cell parametert: a = 1.2390(3), b = 1.1339(2), c = 1.1919 (2) nm and V = 1.6745(6) nm3 with z = 4 for D(c) = 1.39 g.cm-3.The structure was solved by direct method and refined to final R = 0.061 (for 1730 observed reflections). The Space group of 2 is Pna2(1) with unit cell parameters: a = 1.2399(6), b = 1.1371(5), c = 1.1897(2) nm and V = 1.6773(1) nm3 with z = 4 for D(c) = 1.72 g.cm-3, R = 0.038 (for 2157 observed reflections). The X ray structures and IR reveal the bidentate yttrium and ytterbium tetrahydroborate complexes with the intramolecular coordination bonds between lanthanide metal and ligand oxygen atoms.

THE SYNTHESIS AND CRYSTAL-STRUCTURE OF MOLYBDENUM-SILICON BLUE

The single crystal of heteropoly blue, HsSiMo12O40.12H2O, the reduced product of molybdenum-silicon heteropoly acid, was prepared by electrochemical reduction and evaporation in nitrogen atmosphere. The Crystal structure of the product was determined. The heteropoly blue H8SiMo12O40.12H2O, Crystallizes space group P1BAR a = 1.3769 (3) nm, b = 1.4346 (4) nm, c = 1.4134 (4) nm, alpha = 120.47 (2)-degrees, beta = 110.70 (2)-degrees, gamma = 66.11 (2)-degrees, Z = 2, R = 0.0608. The heteropoly blue anion was determined to have Keggin Structure and alpha-isomer and it remained the structure of the unreduced heteropoly acid anion. But the distortion of the structure and the changes of bond length and bond angle take place obviously. The four Mo5+ Positions were determined in the structure.

CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF ERBIUM COMPLEX WITH BENZENE ACETIC ACID

The crystal structure of erbium (III) complex of benzene acetic acid is reported. The complex crystallizes in the monoclinic space group P2(1)/a with a = 0,9008(3)nm, b=1.4242(5) nm, c=1.8437(7) nm, beta=98.80(3)degrees, V = 2.337(1) nm(3), Z = 4. The mechanism of thermal decomposition of complex has been studied by TG-DTG-DTA. The activation energy for dehydration reaction has been calculated by Freeman Carroll method. The enthalpy change for dehydration and phase change process has been determined.

双-(磷酸二甲酯)合锌的结构与光谱

由四圆衍射仪收集标题化合物Zn(DMP)_2的衍射数据。用直接法解出其单晶结构为:空间群Pc,a=0.9361(2),b=1.0519(3).c=1.2028(2)nm. β=91.01(2)°,Z=4.锌原子与4个配体的非酯氧原子形成ZnO_4四面体。具有近似的T_d对称性。相邻锌原子由“O—P—O”桥相连,形成一维链状配位聚合物。红外光谱证实O—P—O基的形成。对某些重要的谱带进行了解释,说明了Zn—O振动与配位阴离子振动的混合情况。

Er_2((PhCH_2COO)_6)·4H_2O的结构及热分析

用X-射线四圆衍射仪测定了Er_2(PhCH_2COO)_6·4H_2O的晶体结构。配合物属于单斜晶系,空间群为P2_1/α,晶胞参数:α=0.9008(3)nm,b=1.4243(5)nm,c=1.8437(7)nm,β=98.80(3)°,V=2.337(1)nm~3,Z=4.采用TG-DTG-DTA研究了配合物的热分解过程,确定了热分解机理。采用Freeman-Carroll方法计算了配合物脱水过程的活化能和反应级数。用DSC测定了配合物脱水,熔化过程的焓变。

Keggin结构钼硅杂多蓝的合成及晶体结构研究

通过电化学还原的方法得到钼硅杂多酸的还原产物杂多蓝单晶H_8SiMo_(12)O_(40)·12H_2O.测完了它的晶体结构.晶体空间群属PI.α=1.3769(3)nm,b=1.4346(4)nm,c=1.4134(4)nm;α=120.47(2)°,β=110.70(2)°,γ=66.11(2)°;Z=2;R=0.0608.确证杂多蓝阴离子呈现Keggin结构和α-异构体特征,基本保持未还原杂多酸阴离子的结构.但是在结构畸变程度、键角和键长的变化以及结晶水的分布上有明显不同.同时确定了杂多蓝阴离子结构中4个Mo~(5+)离子的位置.

氮杂大环钕配合物[Nd(L)(CH_3CN)(CF_3SO_3)_3]的合成和结构

本文报道了三价钕与氮杂大环(简称L)配合物的合成和晶体结构.配合物组成为[Nd(L)-(CH_3CN)(CF_3SO_3)_3],晶体属于三斜晶系,空间群为PI,晶胞参数α=0.8738(2),b=1.2870(3),c=1.2900(3)nm;α=85.63(2),α=87.25(2),γ=78.30(2)°;最终偏差因子R=0.0370,R_w00385.配合物中钕为8配位,其配位多面体为扭曲的四方反棱柱体.