THE COMPATIBILITY AND CRYSTALLIZATION OF THE MIXTURES OF POLY (TETRAHYDROFURAN-b-METHYL METHACRYLATE) DIBLOCK COPOLYMER WITH POLYVINYL CHLORIDE HOMOPOLYMER

The compatibility and crystallization behaviour of the mixtures of poly (tetrahydrofuran-methyl methacrylate) diblock copolymer (PTHF-b-PMMA) with polyvinyl chloride has been studied. We found that the compatibility of these blends, in which there is special interaction between the homopolymer and the PMMA block of the copolymer, is much better than that of the AB/A type blends; and that the crystallization rate and crystallinity of PTHF microdomain changed greatly due to the swollen by PVC homopolymer. In this paper, these changes in cryatallization are well explained according to the theories of block copolymer blends and the density gradient model presented by JIANG Ming.

(C_8H_8)Sm(C_8H_8)Na(THF)_3的晶体结构

(C_8H_8)Sm(C_8H_8)Na(THF)_3的晶体属单斜晶系,P2_1空间群.晶胞参数为α=12.140(3),b=13.794(3),c=8.944(3)(?),β=111.68(3)°,V=1391.8(7)(?)~3,Z=2,μ=21.93cm~(-1),D_c=1.43g/cm~3,F(000)=610,Mr=598.0。结构经Patterson函数和Fourier技术解出并经最小二乘修正,最终的偏离因子R为0.046.配合物具有双层夹心结构.其中Sm~(3+)和Na~+通过η~8-环辛四烯基连接。

(η~5-C_9H_7)_2Yb(THF)_2的晶体结构

双(茚基)镱(Ⅱ)四氢呋喃配合物(η~5-C_9H_7)_2Yb(THF)_2的晶体属单斜晶系,C_c空间群,晶体学参数a=13.506(4),b=11.081(2),c=15.577(5),β=92.68(3)°,V=2329(1),D_c=1.56g/cm~3,Z=4,μ=42.4cm~(-1),F(000)=1088,最终编离因子R=0.029,R_w=0.031。中心离子Yb~(2+)与两个茚基以η~5形式成键且与两个四氢呋喃中的氧成键,茚基的两个质心和四氢呋喃中的两个氧形成扭曲的四面体,Yb~(2+)在四面体的中心。Yb~(2+)的配位数为8。Yb~(2+)到质心In1的距离为2.52,到质心In2的距离为2.40。Yb~(2+)到O(1)的键长为2.356(7),到O(2)的键长为2.417(5)。

SYNTHESIS AND CRYSTAL-STRUCTURE OF ([(C5H9C5H4)ER(THF)]2(MU-2-CL)3(MU-3-CL)2NA(THF)2).THF

The reaction of ErCl3 with one equivalent of C5H9C5H4Na generates the complex {[(C5H9C5H4)Er(THF)]2(mu2-Cl)3(mu3-Cl)2Na(THF)2}.THF, which crystallizes from hexane/THF. The X-ray crystal structure determination shows that each erbium is surrounded by one C5H9C5H4 ligand, two mu3-Cl, two mu2-Cl and one THF in a distorted octahedral arrangement.

SYNTHESIS AND CHARACTERIZATION OF BINUCLEAR ORGANOLANTHANIDE COMPLEXES INVOLVING CYCLOPENTADIENYL AND N-PROPYLOXIDE LIGANDS - X-RAY CRYSTAL-STRUCTURE OF [(C5H5)2YB(MU-OCH2CH2CH3)]2

By the reaction of Cp3Ln (Cp = C5H5; Ln = Dy, Ho, Yb) with equimolar n-propyl alcohol in THF (tetrahydrofuran) at room temperature three new binuclear organolanthanide complexes, [CP2Ln(mu-OCH2CH2CH3)]2 (Ln = Dy, Ho, Yb), have been synthesized, as shown by X-ray single-crystal structure analysis for the complex [Cp2Yb(mu-OCH2CH2CH3)]2. All the complexes were characterized by elemental analysis, IR and MS spectra. The Yb2O2 unit is planar, and the ytterbium atom is coordinated by two Cp ring centroids and two oxygen atoms of two n-propyloxide ligands to form a distorted tetrahedral geometry. The average Yb-C (Cp) bond distance is 2.589(17) angstrom. The average Yb-O distance is 2.199(5) angstrom. The Yb-Yb separation [3.521(1) angstrom] indicates that no metal-metal interaction is present.

SYNTHESIS AND CRYSTAL-STRUCTURE OF (C9H7GDCL2.3THF)THF

The indenylpdolinium dichloride tristetrahydrofuranate (C9H7GdCl2.3THF)THF was prepared and its crystal structure (monoclinic space group P2(1)) determined by X-ray diffraction. In C9H7GdCl2.3THF, Gd, O(1), O(2), O(3) and the centroid of the five-membered indenyl ring form a plane, and Cl(1) and Cl(2) are located at two opposite sides of the plane to give a pseudo-octahedron. The coordination number of Gd is eight.

SYNTHESIS, THERMAL-STABILITY AND X-RAY CRYSTAL-STRUCTURE OF THE BIS(CYCLOPENTADIENYL)YTTERBIUM NAPHTHOXIDE DERIVATIVE (C5H5)2YB(OC10H7)(THF)

Cp3Yb (Cp = C5H5) reacts with a-naphthol (HNP) in THF to form Cp2Yb(NP)(THF) (1), which crystallizes in the space group P2(1)/n with unit cell dimensions a = 8.084(2), b = 15.996(6), c = 15.973(7) angstrom, beta = 98.95(3), V = 2040.3 angstrom and D(calc.) = 1.69 g cm-3 for Z = 4. Least-squares refinement based on 2242 observed reflections converged to a final R value of 0.081. The average Yb-C(Cp) distance is 2.60(2) angstrom and Yb-O(THF) and Yb-O(NP) distances are 2.30(1) and 2.06(1) angstrom, respectively. The title compound loses the coordinated THF molecule readily by heating under vacuum to give dimeric [Cp2Yb(NP)]2 (2), which undergoes disproportionation to give Cp3Yb and Yb(NP)3 on heating above 230-degrees-C.

SYNTHESES OF METHYLCYCLOPENTADIENYL DERIVATIVES OF LANTHANIDES (LN = LA-ND) AND CRYSTAL-STRUCTURES OF [(THF)2LI(MU-CL)2]2[MECPND(THF)] AND [LI(DME)3][MECPLA(NPH2)3]

The reaction of LnCl3.2LiCl with 1 equiv of MeCpNa in THF gives the complexes [(THF)2Li(mu-Cl)2]2[MeCpLn(THF)] (Ln = Nd (1), La (2)) in good yield. These precursors react further with 2 equiv of LiNPh2 to produce the new complexes [Li(DME)3][MeCpLn(NPh2)3] (Ln = La (3), Pr (4), Nd (5)). They have been characterized by elemental analyses and IR and NMR spectra, as well as by structural analyses of 1 and 3. The chloride 1 crystallizes in the monoclinic space group P2(1)/n (No. 14) with a = 12.130 (5) angstrom, b = 17.343 (5) angstrom, c = 17.016 (5) angstrom, beta = 108.54 (3)-degrees, V = 3393.87 angstrom3, Z = 4, and D(c) = 1.45 g/cm3. Least-squares refinement led to a final R value of 0.051 (I greater-than-or-equal-to 3-sigma(I(o))) for 2004 independent reflections. Complex 3 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 18.335 (6) angstrom, b = 16.576 (5) angstrom, c = 17.461 (6) angstrom, beta = 96.04 (3)-degrees, V = 5277.17 angstrom3, D(c) = 1.26 g/cm3, Z = 4, and R = 0.057 (I greater-than-or-equal-to 2.5-sigma(I(o))) for 3378 reflections. The structure of 3 consists of discrete ion pairs [Li(DME)3]+ and [MeCpLa(NPh2)3]- with average La-N and La-C(ring) distances of 2.459 (8) and 2.84 (1) angstrom, respectively.

(η~5-C_5H_5)Ln(η~8-C_8H_8)(THF)_n(Ln=Pr,Nd,Gd)的合成及(η~5-C_5H_5)Pr(η~8-C_8H_8)(THF)_2的晶体结构

自1969年首次报道稀土环辛四烯基化合物Eu(C_8H_8)和Yb(C_8H_8)的合成以来,相继合成K[Ln(C_8H_8)_2],[Ln(C_8H_8)Cl·2THF]_2和[Ln(C_8H_8)·2THF]等,还报

(C_5H_9C_5H_4)_2 LnCl·nTHF的合成及[(C_5H_9C_5H_4)_2SmCl(THF)]_2和[(C_5H_9C_5H_4)_2ErCl]_2的晶体结构

1980年以来,取代环戊二烯基稀土配合物化学取得了较快的发展,合成了许多取代环戊二烯基稀土氧化物。这些大体积的配体如—C_5Me_5—(Me_3Si)_2C_5H_5-t-BuCp等,可以稳定低配位数的络合物,特别是单或双取代的环戊二烯基稀土氯化物。我们用环

SmCl_3(THF)_4的晶体结构

标题化合物SmCl_3(THF)_4(M_r=545.2)晶体属正交晶系,空间群为Pdd 2。晶胞参数为a=9.211(4),6=16.436(6),c=29.666(12);V=4491(3) ~3;Z=8,D_c=1.61g.cm~(-3),F(000)=2184,μ_c=30.3cm~(-1)。最终的偏因子R=0.063,R_(to)=0.062。Sm~(3+)与三个Cl~-及四个四氢呋喃分子中氧原子配位,形成一个五角双锥的空间结构,其中二个氯原子分别位于二个顶点位置。分子中有一个通过Sm~(3+)及Cl~-的C_2轴。Sm-Cl及Sm-0的平均键长分别为2.683(5)及2.469(11)。

[Cp_2ErCl(THF)]_2的晶体结构

本文报导了(Cp_2ErCl(THF)]_2的晶体结构,晶体属单斜晶系,P2_1/c空间群。晶胞参数为a=8.141(2),b=21.218(6),c=8.597(2),β=107.77(2)°;V=1414.1(6) ~3;Z=2,D_c=1.90g/cm~3,F(000)=780,μ_c=66.3cm~(-1)(MoK_a)。最终的偏离因子R=0.047,R_(to)=0.048。结构分析表明,该配合物是以两个氯离子与金属离子桥联的二聚体形式存在。四氢呋喃中的氧原子同金属离子键合,Er—O键长为2.490(6),两个环戊二烯中的所有碳原子同金属离子间的平均键长为2.649,Er-Cl=2.666(3),Er—Cl-a=2.797(3),Er-Er_a=4.42,Cl-Er-Cl_a键角为72.2°。

[Li(THF)_4][GdCl_4(THF)_2]的晶体结构

氯化钆与对-甲基苯基锂在四氢呋喃中反应得到产物之一为[Li(THF)_4][GdCl_4-(THF)_2],(M_r=738.2),在-70℃下进行X-射线衍射研究。其晶体属单斜晶系,P2/n空间群。晶体学参数为a=13.263(2),b=8.474(1),c=14.961(0);β=99.72(1)°,V=1657.23(?)~3,Z=2,D_c=1.48g/cm~3,F(000)=750,μ_c=24.2cm~(-1),最终偏离子为R=0.0614。研究结果表明,本题晶体是离子型晶体,围绕Gd~(3+)的四个Cl~-离子和两个THF分子的氧原子构成畸变的八面体。Li~+周围的四个THF分子的氧原子构成一个近似的四面体。

(η~5-C_5H_5)_2Yb(THF)_2的新合成方法及其晶体结构

双(环戊二烯基)镱(Ⅱ)四氢呋喃配合物(η~5-C_5H_5)_2Yb(THF)_2通过环辛二烯基钾(KC_8H_(11))还原(C_5H_5)_2YbCl·THF而得到,经元素分析、红外光谱表征,并测定了其晶体结构。配合物属单斜晶系,C2/c空间群,晶体学参数a=1.3564(4),b=0.9569(3),c=1.4747(6)nm;β=109.90(3)°;V=1.79975(118)nm~3;D_c=1.65·cm~(-3);μ_C=54.7cm~(-1)(Mo);F(000)=880,Z=4。最后一致性因子R=0.079,R_w=0.081。Yb~(2+)的配位数为8。