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.

STRUCTURE OF 1,10-DIAMINODECANE TETRACHLOROZINCATE

[NH3(CH2)10NH3][ZnCl4], M(r) = 381.51, triclinic, P1BAR, a = 7.296 (1), b = 10.110 (3), c = 12.814 (4) angstrom, alpha = 90.84 (2), beta = 101.17 (2), gamma = 92.52 (2)-degrees, V = 926.13 angstrom 3, Z = 2, D(x) = 1.37 Mg m-3, lambda(Mo K-alpha) = 0.71073 angstrom, mu = 1.925 mm-1, F(000) = 396, T = 298 K, final R = 0.070 for 1237 unique reflections [I > 3-sigma(I)]. The structure is characterized by layers of inorganic ions sandwiched between layers formed by the paraffinic chains.

STRUCTURE OF 1,3-PROPANEDIAMMONIUM TETRACHLOROCOBALTATE(II)

[CoCl4(C3H12N2)], M(r) = 276.87, monoclinic, P2(1)/n, a = 10.703 (2), b = 10.653 (1), c = 10.852 (2) angstrom, beta = 118.46 (1)-degrees, V = 1087.8 angstrom 3, Z = 4, D(x) = 1.69 g cm-3, lambda(Mo K-alpha) = 0.71073 angstrom, mu = 22.60 cm-1, F(000) = 556, T = 298 K, final R = 0.059 for 1068 unique reflections [I > 3-sigma(I)]. The Co(II) ion is coordinated by four Cl atoms in a tetrahedral geometry. The paraffinic chains which bridge the tetrahedra have a nearly planar zigzag configuration.

INFRARED SPECTRA AND CRYSTAL STRUCTURE OF BIS-(DIMETHOXYLPHOSPHATO) COPPER

The title complex has beep synthesized by the reaction of CaCl2, with trimethyl phosphate. Its Infrared spectra from 4000 to 100 cm(-1) measured. The assignment of acme absorption bands was discussed. It is found that the stretching vibrations of bridge groups O-P-O are divided into two groups according to their bond length. The crystal structure of the complex boa been determined from single crystal K-ray diffraction data. The crystals belong to monoclinic system, space group P2(1)/c with cell parameteras, a = 1,0704(4), b = 0.5093(2), c = 1.9737(6)nm, beta = 96.23(3)degrees, V = 1.0696(6)nm(2), Z = 4, final R = 0.044. Copper ion is coordinated to five Rimester oxygen atoms to form a distorted square pyramid. The adjacent copper ions are connected by symmetric and non-symmetric bridge groups of O-P-O, forming an infinite one-dimensional chain coordination polymer.

{MoOS_3Cu_3(PPh_3)_3Cl}的合成及晶体结构

本文合成并测定了{MoOS_3Cu_3(PPh_3)C1}的晶体结构,簇合物属正交晶系,空间群为P_(212121)晶胞参数:a=12.833(5)×10~(-10)m,b=17.552(5)×10~(-10)m,c=22.778(7)×10~(-10)m;Z=4。结构用直接法解出,经最小二乘法修正,偏离因子R=0.069.

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.

镧系金属有机配合物的研究 XL.双(2-甲氧乙基环戊二烯基)钇和镱的硼氢配合物的合成及晶体结构

双(2-甲氧乙基环戊二烯基>氯化钇和镱,在THF中,室温与硼氢化钠发生置换反应,生成双(2-甲氧乙基环戊二烯基)硼氢化钇(1)和镱(2),产率分别为70和59%.它们都经红外光谱,质谱,~1HNMR和元素分析鉴定.将l和2在THF-已烷中重结晶,得到适用于X射线衍射分析的单晶.1的空间群为Pna2_1,晶胞参数:a=1.2390(3),b=1.1339(2),c=1.1919(2)nm,晶胞体积,1.6745(6)nm~3.D_o=1.39g·om~3,z=4,R=0.061;2的空间群为Pna2_1,晶胞参数:a=1.2399(6),b=1.1371(5),c=1.1897(2)nm,晶胞体积,1.6773(1)nm~3,D_c=1.72g·cm~(-3),z=4,R=0.038,1与2都是含有两个内配位键(Ln—O)的双齿型的单体结构.

三碘-氯化四-(4-三甲基苯胺基)卟啉-羟基-水合锰水合物的合成与晶体结构

报道了标题化合物([Mn(Ⅲ)OH·H_2O·TMAP]·I_3·Cl·9H_2O)的合成和晶体结构。晶体属P2_(1/a)空间群,a=1.8502(1)nm,b=1.2738(1)nm,c=3.0458(2)nm,β=104.52(4)°,Z=4,R=0.096,R_w=0.087.用顺磁和光谱电化学证明卟啉配合物中心锰为三价,确定了锰卟啉轴向两个配位氧原子,一个属水分子,另一个属氢氧根。讨论了锰卟啉的稳定氧化态。

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_9H_7)_3Ln·OC_4H_8(Ln=Nd、Gd、Er)的合成及晶体结构

合成了三茚基稀土配合物(η~5-C_9H_7)_3Ln·OC_4H_8(Ln=Nd、Gd、Er),经元素分析、红外光谱、水解产物核磁共振谱及质谱表征,并测得了(η~5-C_9H_7)_3Nd·OC_4H_8(1)及(η~5-C_9H_7)_3Gd·OC_4H_8(2)的晶体结构。(1)、(2)均属六方晶系,P6_3空间群,Z=2。(1)的晶体学参数为a=b=1.1843(3)nm,c=1.0304(4)nm,V=1.25165(87)nm~3,D_c=1.49g·cm~(-3),最后一致性因子R=0.049;(2)的晶体学参数a=b=1.1805(2)nm,c=1.0236(2)nm,V=1.23536(56)nm~3,D_c=1.54 g·cm~(-3),R=0.023。平均Nd-C=0.2812nm,Gd-C=0.2795nm;Nd-O=0.2557(21)nm,Gd—O=0.2459(13)nm。配合物中四氢呋喃的四个碳原子处于完全无序状态。

(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。

[Li(THF)_4][Nd(C_8H_8)_2]·2THF的合成及晶体结构

无水NdCl_3与甲基萘锂以1:2摩尔比在THF中反应分离得到一种黑色产物,该产物与环辛四烯反应,分离得到标题化合物,测定了这一新配合物的晶体结构。该晶体属单斜晶系,空间群P2/c,晶胞参数a=1.7858(7)nm,b=1.3243(4)nm,c=1.8085(6)nm,β=106.52(4)°,V=4.10nm~3,D_c=1.268 g/cm~3,Z=4,F(000)=1660,R=0.0774,R_w=0.0733。配合物分子由不相连的阴阳离子对组成,阴离子是由中心钛离子与二个对称的环辛四烯组成,阳离子是由一个锂离子和四个THF分子配位而成,另有二个THF分子作为填充分子存在于晶胞中。