Synthesis, characterization and crystal structures of dibenzo-18-crown-6 sodium isopolytungstates

Two novel dibenzo-18-crown-6 sodium isopolytungstates, [(DB18C6)(CH3OH)Na](2)W(6)O(19)(.)DB18C6(.)H(2)O 1 and [(DB18C6)(DMF)(2)Na](4)W(10)O(32)(.)2DMF(.)2H(2)O 2, have been synthesized in mixed methanol and acetonitrile solvents and characterized by elemental analysis, TGA, IR and single crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic space group C2/c with a = 23.182(8), b = 19.527(2), c = 18.737(3) Angstrom, beta = 115.15(2)degrees, V = 7678(3) Angstrom(3), Z = 4, and R1(wR2) = 0.0611(0.1504). The compound 2 crystallizes in the monoclinic space group P21/n with a = 16.516(2), b = 22.325(6), c = 20.425(7) Angstrom, beta = 91.78(2)degrees, V = 7528(3) Angstrom(3), Z = 2, and R1(wR2) = 0.0397(0.0773). The compound 1 exhibits a novel organic-inorganic sandwich-type structure, in which the crown ether-sodium complexes are coordinated to the terminal oxygen atoms of W6O192-. In compound 2, all Na+ ions are thoroughly enveloped into the organic moieties of crown ether and DMF molecules and are connected with the 'naked' polyanions W10O324- via the electrostatic attraction.

Hydrothermal synthesis, crystal structure and properties of [HPDA][H(2)PDA](2)[As-2(III)-AsMo8V4O40]center dot 3H(2)O (PDA = propane diamine)

[NH3CH2CH2CH2NH2][NH3CH2CH2CH2NH3](2)[(As2AsMo8V4O40)-As-III-Mo-V-O-IV].3H(2)O was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data: monoclinic, C2/c, a = 45.375(9) Angstrom, b = 11.774(2) Angstrom, c = 23.438(5) Angstrom, beta = 96.62(3)degrees. X-ray crystallographic study showed that the crystal structure was constructed by bicapped alpha-Keggin fragments [(As2AsMo8V4O40)-As-III-Mo-V-O-IV](5-) polyoxoanion. The title compound had a high catalytic activity for the oxidation of benzaldehyde to benzoic acid using H2O2 as oxidant in a liquid-solid biphase system.

不对称型双核半夹心结构铁化合物Cp′_2Fe_2(CO)_3Se_2C_2B_(10)H_(10)(Cp′=η~5-C_5H4Me)的合成、表征及结构

用碳硼烷的含硒锂盐 Li2 Se2 C2 B1 0 H1 0 (1 )与单茂羰基铁的氯化物 Cp′ Fe(CO) 2 Cl(2 )反应得到不对称型双核半夹心结构铁的化合物 Cp′2 Fe2 (CO) 3Se2 C2 B1 0 H1 0 (3 ) .X射线单晶结构分析表明其中一个铁原子是手性的 ,而且两个铁原子之间没有相互作用

高温高压法提取金属富勒烯Ln_m@C_(2n)(Ln=Y,Gd,Tb)

笼内金属富勒烯以其独特的结构性质和潜在的应用价值而引起了人们极大的注意 [1～ 3] ,但因制备技术复杂、产率低以及将其从伴生的空心富勒烯中分离出来比较困难而使其研究受到很大的限制 .笼内金属富勒烯的分离提取始终是金属富勒烯研究的一个重要分支 .通常的方法是将放电得到的烟炱采用甲苯索氏提取的方法粗提 ,然后用高压液相色谱法分离得到纯品 ,笼内金属富勒烯的产率仅为烟炱的 0 .1 % [4～ 6] .我们改进了常规的提取方法 ,建立了一种新的提取方法—高温高压提取法 .具体的做法是采用甲苯索氏提取法从烟炱中提取出空心富勒烯和少量金属富勒烯 ,对剩余物用 1 ,2 ,4-氯苯高温高压法提取 .笼内金属富勒烯的产率增大了 5倍 ( 0 .5 % ) ,这一结果目前尚未见文献报道 .1　实验部分1 .1　金属富勒烯的合成　笼内金属富勒烯 Lnm@C2 n( Ln=Y,Tb,Gd)采用电弧放电法 ,在自制的一套电弧放电器中合成 .将 8mm× 2 0 0 mm的光谱纯级石墨棒钻出 5 mm× 1 5 0 mm的深孔 ,充填经预先处理的各种稀土氧化物和石墨粉的混合物 ,混合物中稀土原子和碳原子物质的量比为 1∶ 5 ...

梳状聚合物电解质的力学松弛时间

以苯乙烯 /马来酸酐共聚物为骨架 ,聚乙二醇单甲醚为侧链合成了 3种不同侧链长度的梳状高分子聚合物 ,制成了锂盐络合物薄膜 .动态力学性能研究结果表明 ,本体系是主链刚性、侧链较柔软的梳状接枝聚合物 .应用时间温度等效原理 ,选择Tα 作为参考温度 ,建立了主曲线 ,得到了移动因子图和等自由体积图 .Williams、Landel和Ferry(WLF)经验方程的两个参数C1、C2 随着盐浓度增加而增大 .若T0 =50℃作为参考温度 ,平均松弛时间lgτc 与锂盐浓度C呈线性关系 .随着侧链分子量增加 ,主曲线向高频率移动 ;平均松弛时间lgτn 与侧链分子量的关系也是线性的 ;另外随着盐的不同 ,主曲线也会产生移动 ,表明盐种类对松弛时间产生影响.

稀土催化丁二烯-异戊二烯共聚合过程中的原位环化反应

采用 Nd( naph) 3- Al( C2 H5) 3- ( t- C4 H9) Cl三组分稀土催化剂进行丁二烯 ( BD) -异戊二烯( IP)的顺式共聚合 ,在聚合过程中引入有机氯代烃 ( RCl) ,以与聚合液中的烷基铝作用生成阳离子活性种 ,引发已生成的共聚物的环化反应及单体的环聚反应 ,得到可溶性无凝胶且含有环聚成分的环化共聚合产物 .考察了 RCl用量、单体组成、稀土催化剂用量、反应温度等对原位环化反应的影响 .以红外光谱、核磁共振光谱对环化产物的结构进行了初步分析 ,确认了环化产物的生成

Hydrothermal synthesis and structure of a bi-capped Keggin polyoxoanion, [(As2AsMo8V4O40)-As-III-Mo-V-O-IV](5-)

The title compound, [NH3CH2CH2CH2NH2][NH3CH2CH2CH2NH3](2)[As-2(III) As-v Mo-8 V-4(IV) O-40] (.) 5H(2)O, was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data: monoclinic, C2/c, a = 45.375(9) Angstrom, b = 11.774(2) Angstrom, c = 23.438(5) Angstrom, beta = 96.62(3)degrees. X-ray crystallographic study showed that the crystal structure was constructed by bi-capped alpha -Keggin fragments [(As2AsMo8V4O40)-As-III-Mo-v-O-IV](5-) polyoxoanion. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis and crystal structure of a novel compound: [H3PMo12O40][CO(NH2)(2)](3)center dot-5H(2)O

The title compound, [H3PMo12O40][CO(NH2)(2)](3). 5H(2)O, was synthesized and characterized by IR, C-13 NMR and X-ray diffraction. This is the first example of a urea-heteropoly acid species. Crystal data: monoclinic, C2/c, a = 17.790(4) Angstrom, b = 17.158(3) Angstrom, e = 25.512(5) Angstrom, beta = 100.65(3)degrees, V = 8514(3) Angstrom (3), Z = 6, R-1 = 0.0437, wR2 = 0. 1092. In the unit cell, the urea molecules occupy cavities in the polyoxometalate lattice ordered along b-axis. Water molecules occupy the space left by polyoxometalates, and urea. Polyoxometalate O atoms, the N atoms of urea and O atoms of water molecules are involved in hydrogen bonding. (C) 2001 Elsevier Science B.V. All rights reserved.

Interactions of thiamine with anions: (Hthiamine)(thiamine) heptaiododimercurate dihydrate and its dimethanol monohydrate

In the title compounds, 3-[(4-amino-2-methyl-5-pyrimidinio)methyl] -5-(2-hydroxyethyl)-4-methylthiazolium(2+) 3-[(4-amino-2-mcthyl-5-pyrimidinyl)methyl]-5-(2-hydroxyethyl)-4-methylthiazolium( 1+) heptaiododimercurate dihydrate, (C12H18N4OS)(C12H17N4OS)[Hg2I7]. 2H(2)O, (I), and its dimethanol monohydrate, (C12H18N4OS)(C12H17N4OS)[Hg2I7]. 2CH(3)OH . H2O (2), a crystallographic centre of symmetry in (1) or a twofold axis in (2) is imposed between the protonated and deprotonated thiamine molecules, resulting in a statistically half-occupied proton attached at N1' of the pyrimidine ring. The Hg2I73- anion, residing on the centre of symmetry in (1) or on the twofold axis in (2), interacts with two thiamine molecules, each through a C2-H ... I ... pyrimidine-ring interaction. This bridging interaction is a characteristic of thiamine in the F conformation.

Theoretical investigation of small lathanum carbide clusters

LaC2+, LaC22+, LaC3 and LaC3- clusters have been studied using B3LYP density functional method. Four isomers with C-2v, C-s, C-infinity v and D-infinity h symmetry were presented for LaC2+ and LaC22+. Meanwhile, two spin states, namely, singlet and triplet for LaC2+, doublet and quartet for LaC22+ were considered The results indicated that ring isomers with C-2v and C-s symmetry are the most stable for La-C2(+) at both spin states and for LaC22+ at quartet state. Whereas for LaC22+ at doublet state, linear isomer with C-infinity v symmetry is energetically favored, For LaC3 and LaC3- clusters,, three isomers have been presented for each cluster, that is, two ring isomers with C-2v symmetry ( in one of them, La forms two single bonds with two carbons, and in another, La forms a double bond with carbon), and one linear isomer with C-infinity v symmetry. The results revealed that the ring isomer in which La forms two single bonds with carbons is the lowest in energy.

1,4-二丙氧基-2,3二氰基萘的晶体结构

用 Siemens P4四圆衍射仪,测得了1,4-二丙氧基-2,3-二氰基萘的晶体结构。晶体属单斜晶系,空间群为 C2/C。晶格参数 a=14.987(3)A,b=10.527(2),c=11.755(2),β=118.98°(3),晶胞体积 V=1622.4(6)3,Z=4,Dc=1.205Kg/m~3,μ(MoK_α)=0.079mm~(-1),F(000)=624,T=293(2)K_o晶体结构应用直接法,解出最后的偏离因子 R=0.0554[1425个Ⅰ≥2σ(Ⅰ)衍射点]。结构分析表明,萘环的1,4和2,3位碳原子上的氢原子分别被丙氧基和氰基所取代,由于取代基的引入使萘环的结构有所改变。

Influences of acid treatments of active carbons on no reduction over carbon-supported copper oxides

Active carbon supported copper oxides were used in NO reduction. The conversions of NO reduction depends strongly on surface oxygen-containing groups on the active carbons, among them the carboxyls and lactones favored remarkably the NO reduction. However, hydrochloric acid treatment led to the decomposition of the carboxyls and lactones on C2 and C3, decreasing their reactivities for NO reduction. Concentrated HNO3 treatment of active carbon produced higher conversions of NO reduction at relatively low temperatures due to the marked increase in the amounts of the carboxyls and lactones.

Syntheses and reactions of heterometallic complexes of nickel and copper with tetrathiotungstates. The molecular structures of [Ph(4)P](2)[S2W(mu-S)(2)Ni(S-2)] and W(mu-S)(4)Cu-2(PPh(3))(4)center dot py

Reaction of [Ph(4)P]2WS4 With NiCl2 in methanol solution in the presence of NaOCH3 leads to the formation of [Ph(4)P](2) [S2W(mu-S)(2)Ni(S-2)] (I) A Similar reaction between (NH4)(2)WS4 and NiCl2 under O-2 atmosphere in the presence of Ph(4)PCl or (n)Bu(4)NCl affords [Ph(4)P](2)([(S-2)W(O)(mu-S)(2)]Ni-2] (IIa) and [(n)Bu(4)N](2)([(S-2)W(O)(mu-S)(2)]Ni-2} (IIb) Under argon the same reaction gives [Ph(4)P](2)[Ni(WS4)(2)] (IIIa) and [(n)Bu(4)N](2)[Ni(WS4)(2)] (IIIb). [Ph(4)P](2)[Ni(WOS3)(2)] (IV) and [Ph(4)P](2)[Ni(WO2S2)(2)] (V) can be prepared from the reaction of [Ph(4)P]2WOS3 and [Ph(4)P]2WO2S2 with NiCl2. Treatment of (NH4)(2)WS4 with CuCl in the presence of PPh(3) in boiling pyridine produces W(mu-S)(4)Cu-2(PPh(3))(3) (VI), which can further react with excess PPh(3) to give W(mu-S)(4)Cu-2(PPh(3))(4) . py (VII). Complex I crystallizes in the space group P2(1)/n with the cell parameters: a = 20.049(4), b = 17.010(4), c = 14.311(7) Angstrom; beta = 110.24(3)degrees and Z = 4; R = 0.058 for 4267 independent reflections. The structural study confirms that complex I contains two terminal sulfide ligands, two bridging sulfide ligands, a side-on disulfide ligand, and a planar central W(mu-S)(2)Ni four membered ring. Complex VII crystallizes in the space group C2/c with the cell parameters: a = 26.436(8), b = 20.542(6), c = 19.095(8) Angstrom; beta = 125.00(3)degrees and Z = 4; R = 0.080 for 3802 independent reflections. The structural study reveals a perfect linear arrangement of the three metal atoms Cu-W-Cu.

Synthesis and molecular structures of di- and trinuclear molybdenum complexes containing pyridine-2-thiolato (pyS) ligand

Dinuclear complexes [Mo-2(mu-pyS)(2)(CO)(4)(PPh(3))(2)] (1), [Mo-2(mu-pyS)(2)(CO)(5)(PPh(3))] (2) and a trace quality of trinuclear complex [Mo-3(mu-pyS)(2)(mu(3)-pyS)(2)(CO)(6)] (3) were obtained from the reaction of [Mo(CO)(3)(MeCN)(3)] with pyridine-2-thione (pySH) and PPh(3) in THF. The crystal structures of 1.2C(7)H(8) and 3.7 C7H8 have been determined by X-ray diffraction studies. Crystals of 1.2C(7)H(8) are monoclinic, space group C2/c and Z = 4, with a = 18.797(3), b = 11.143(4), c = 28.157(7) Angstrom, beta = 101.23(2)degrees. The structure was refined to R = 0.050 and Rw = 0.057 for 3146 observed reflections, Crystals of 3.7 C7H8 are monoclinic, space group P2(1)/a and Z = 4, with a = 13.912(2), b = 17.161(2), c = 15.577(3) Angstrom, beta = 101.17(1)degrees. The structure was refined to R = 0.046 and Rw = 0.051 for 4357 observed reflections. The molecule of 1 consists of two Mo(CO)(2)(PPh(3)) fragments linked by an Mo-Mo bond (2.974(2)Angstrom) and by two doubly-bridging pyS ligands. The compound 3 contains a bent open geometry of three molybdenum atoms (Mo(1)-Mo(2)-Mo(3) angle 122.99(3)degrees) linked by two Mo-Mo bonds (2.943(1) and 2.950(1) Angstrom) and by two doubly- and two triply-bridging pyS ligands.

The reactivity of lanthanide alkyl compounds with phenylacetylene: Synthesis and structure of [(Bu(t)Cp)(2)LnC CPh](2) (Ln=Nd, Gd)

[(Bu(t)Cp)(2)LnCH(3)](2) (Ln = Nd, Gd) react with PhC=CH to form the dimeric alkynide-bridged complexes [(Bu(t)Cp)(2)LnC=CPh](2) [Ln = Nd (I), Gd (II)]. Both compounds crystallized from toluene in the monoclinic space group C2/c. The two complexes are homologous, composed of asymmetric metal-alkynide bridges with Nd-C, Gd-C (alkynide) bond lengths of 2.602(4), 2.641(5) (I) and 2.532(6), 2.601(7) Angstrom (II), respectively. The average Nd-C (ring) and Gd-C (ring) distances are 2.746(13) and 2.703(19)Angstrom.