同多和杂多阴离子的有机衍生物

同多和杂多阴离子的有机衍生物是一类新型的催化剂,并可用作电子显微镜的染色剂,还可标记有机化合物的特殊官能团或大分子的生物活性部分。自1975年以来,对它的研究已成为多酸化学中极其活跃的领域叫。由于有机配位体纷繁多样,十余年来,合成的新化合物层出不穷。至今已制备出原子数超过500的单一分子和分子量约为10~6的高分子聚合物。近几年     

具有Keggin和Dawson结构的钨钼杂多阴离子的有机衍生物及其应用

自从1913年Rosenheim和Bilecki首次报道含有机基团的杂多化合物后,直到1978年第一个具有Keggin结构杂多阴离子的有机衍生物才被研制出来,此后文献上相继报道了各种类型杂多阴离子的有机衍生物。由于它们是一类十分优秀的催化剂,可用于电子显微镜的染色剂、光电有机调色剂、标记有机化合物的特殊官能团或大分子的生物活性部分,在印     

三缺位杂多阴离子α—A—PW9O34^9—的苯基硅衍生物的合成和晶体结构

合成了三缺位杂多阴离子的苯基硅衍生物 (TBA) 3[α-A-PW9O34 (Ph Si O) 3(Ph Si) ]· 2 H2 O(记为 1 ,TBA为四丁基铵阳离子 ) ,并由元素分析、红外光谱、紫外光谱对化合物进行了表征 ,研究了化合物的热性质 .结构分析结果表明 ,该化合物属三方晶系 ,空间群 R3,晶胞参数 a=1 .41 696(1 6) nm,b=1 .42 1 63 (1 6)nm,c=1 .41 661 (1 6) nm,α=99.80 1 (1 7)°,β=99.843 (1 7)°,γ=99.844(1 7)°,V=2 .71 1 1 (5 ) nm3.Z=1 ,R=0 .0 5 48.该化合物的阴离子是由 1个α-A-PW9单元 ,通过 6个 W— O— Si桥键与 3个 Ph Si O单元相连 ,3个 Ph Si O又通过 Si— O— Si桥键与另 1个处于帽位的 Ph Si相连 ,形成饱和闭合笼形结构     

三缺位α-9钨镓杂多酸盐的合成与性质

本文报道了一种新的三缺位杂多阴离子α-[GaW_9O_(34)H_2]~(9-)的钠、钾、四甲基铵盐的合成方法,并通过元素分析、红外、紫外、极谱、热分析等方法对它进行了表征。α-[GaW_9-O_(34)H_2]~(9-)是一具有三个空位的杂多阴离子,它能与过渡金属离子反应生成具有Keggin结构的三取代钨镓杂多阴离子[GaW_9O_(37)M_3(H_2O)_3]~(R-)。     

三缺位杂多阴离子α-A-PW9O9-34的苯基硅衍生物的合成和晶体结构

合成了三缺位杂多阴离子的苯基硅衍生物(TBA)3[α-A-PW9O34(PhSiO)3(PhSi)]*2H2O(记为1, TBA为四丁基铵阳离子), 并由元素分析、红外光谱、紫外光谱对化合物进行了表征, 研究了化合物的热性质. 结构分析结果表明, 该化合物属三方晶系, 空间群R3, 晶胞参数a=1.416 96(16) nm, b=1.421 63(16) nm , c=1.416 61(16) nm, α=99.801(17)°, β=99.843(17)°, γ=99.844(17)°, V=2.711 1(5) nm3. Z=1, R=0.054 8. 该化合物的阴离子是由1个α-A-PW9单元, 通过6个W-O-Si桥键与3个PhSiO单元相连, 3个PhSiO又通过Si-O-Si桥键与另1个处于帽位的PhSi相连, 形成饱和闭合笼形结构.     

钨硅杂多阴离子二聚体的合成及表征

单氧桥双铁化合物L_5Fe—O—FeL_5已有报道.但有关含杂多阴离子的桥氧二聚体XM_(11)M′—O—M′XM_(11)的报道则甚少.本文合成了3种杂多阴离子二聚体(SiMW_(11))_2O(M=Fe~(Ⅲ),Cr~(Ⅲ),Al~(Ⅲ)),并用XPS、UV、IR及磁化率测定等手段对其性质进行了研究.     

Keggin三取代型杂多阴离子183W NMR化学位移的特征模式＊

The reaction of SiW₉O^10-₃₄ and GeW₉O^10-₃₄ with metal cations leads to Keggin trisubstituted polyoxoanions.A review of all known trisubstituted Keggin anions demonstrates characteristic patterns of ¹⁸³W NMR chemical shifts.     

Keggin三取代型杂多阴离子183W NMR化学位移的特征模式

三空位杂多阴离子ＳｉＷ９Ｏ１０－３４有α和β两种异构体［１］,β－ＳｉＷ９Ｏ１０－３４阴离子钠盐的晶体结构测定表明,它是β－ＳｉＷ１２Ｏ４－４０阴离子的缺位衍生物,是从β－ＳｉＷ１２Ｏ４－４０阴离子中去掉３个ＷＯ６八面体后形成的含３个空位的杂多阴离子...     

钨硅系列三元杂多阴离子柱撑阴离子粘土的合成及表征

采用离子交换法将过渡金属离子三元取代钨硅杂多阴离子引入Zn₂Al型阴离子粘土层内，得到柱撑水滑石Zn₂Al(OH)₆-SiW₉Z₃O₄₀(Z=Ti⁴⁺, Mo⁶⁺)及Zn₂Al(OH)₆-SiW₉Fe₃(H₂O)₃     

三个基于Wells-Dawson型多酸的三核铜簇的合成、结构及性能

在水热条件下,通过Wells-Dawson型多酸[As_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(4-吡啶基)-1H-四氮唑(4-ptz)的反应,在同一反应釜中合成出2个结构完全不同的、都包含三核铜簇的多酸基化合物[Cu3(4-ptz)4(H_2O)7(As_2W_(18)O_(62))]·42H_2O(1)和[Cu3(4-ptz)5(H_2O)5(As_2W_(18)O_(62))]·47H_2O(2);当我们以另一种Wells-Dawson型多酸[P_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(3-吡啶基)-1H-四氮唑(3-ptz)反应,获得了另一种多酸基三核铜簇化合物[Cu3(3-ptz)4(H_2O)8(P_2W_(18)O_(62))]·33H_2O(3)。X射线单晶衍射结果表明,化合物1为多酸单支撑三核铜簇的悬臂式结构,化合物2的多阴离子被三核铜簇交替连接形成一维链式结构,而化合物3为多阴离子和三核铜簇形成的孤立结构。吡啶-四氮唑类配体(3-ptz和4-ptz)是形成化合物1~3中三核铜簇的重要结构因素。同时,研究了3个化合物的电化学以及光催化性能。     

Electrochemical study of isopoly and heteropoly anion transfer across the water | nitrobenzene interface. Part II. Vanadium-containing heteropolytungstate anions

The electrochemical transfer behaviour of vanadium-containing heteropolytungstate anions [PW_12−xV_xO₄₀]^(3+x)− (x = 1−4) across the water | nitrobenzene interface has been investigated by cyclic voltammetry and chronopotentiometry with cyclic linear current scanning. The transfer of PW₁₁V₁O⁴⁻₄₀, HPW₁₀V₂O⁴⁻₄₀, H₂PW₁₀V₂O³⁻₄₀, H₃PW₉V₃O³⁻₄₀ and H₄PW₈V₄O³⁻₄₀ across the water | nitrobenzene interface can be observed within the potential window. The effects were observed of pH in the water phase on the transfer behaviour and the formation of vanadium-containing heteropolytungstate anions in solution. Heteropolytungstate anions become more stable due to their involving the vanadium atom. The degree of protonation and the dissociation constant of the trivalent vanadium-containing heteropolytungstate anion of protonation increase with increasing vanadium content. The transfer processes are diffusion-controlled. The standard transfer potential, the standard Gibbs energy and the dissociation constant for vanadium-containing heteropolytungstate anions have been obtained and the transfer mechanisms are discussed.     

碱土金属钨铬杂多配合物的合成、表征及热稳定性研究

用直接法合成了以Cr为中心原子的碱土金属和W的三元杂多配合物,经ICP和TG曲线确定其化学式为K7[CrA(H2O)W11O39].xH2O(A=Mg2 ,Ca2 ,Sr2 和Ba2 ),采用IR,UV,XRD,XPS和183W NMR等手段对配合物结构进行了表征,确认所合成的配合物为-αKeggin结构.借助TG-DTA详细讨论了配合物的热稳定性,得出合成配合物的热稳定温度为450℃左右.     

A study of complexation of chloral hydrate with heteropoly anions having various structures

¹H NMR was applied to study the interaction of chloral hydrate in deuterionitrobenzene solution with tetrabutylammonium salts of the heteropoly acids (HPA) belonging to five structural types: Keggin (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, H₄SiW₁₂O₄₀), Dawson (-H₆P₂W₁₈O₆₂, -H₆P₂Mo₁₈O₆₂, -H₄S₂Mo₁₈O₆₂), H₆P₂W₂₁O₇₁(H₂O)₃, H₆As₂W₂₁O₆₉(H₂O), and H₂₁B₃W₃₉O₁₃₂. The surface of the HPA anions is nonuniform in acid-base properties. A general rule for all HPA was found, namely, that the HPA acidity increases with a decrease in the specific anion charge (per W or Mo atom).     

Anderson型杂多酸-DABCO复合二维相变晶体材料的合成及介电性质

以1.4-二氮杂二环[2.2.2]辛烷(DABCO)氟硼酸盐与(NH4)3[FeMo6 O24 H6]·7H2 O多酸盐为原料,通过H管水溶液界面扩散方式合成一种新颖的Anderson型超分子化合物(H2 DABCO)2[FeMo6 O24 H4]·4H2 O(1).并通过红外光谱、单晶X衍射、元素分析、XRD粉末衍射...     

Electronic structure of cesium and thallium triple-decker anions

Cesocene [Cp₃Cs₂]− and thallocene [Cp₃Tl₂]− triple-deckers have been recently synthesized. The X-ray structure analysis in solid state phase shows that both compounds have a strong bent structure, Cp centroid–M–Cp´ centroid (M=Cs or Tl) angles are 115.6° and 134.2°, respectively. In this work we report the theoretical study of these new compounds using Gaussian 94 at B3LYP level, with a 6-31G* basis for all atoms, except Cs and Tl, for which a LANL2DZ basis set is considered. Our results show that in gas phase, thallocene presents a bent structure while cesocene does not. However, using a force field method, we prove that in solid state phase the cesocene becomes bent due to the interaction between neighbors, in agreement with experimental data.     

两个新的Dowson结构硫钼多酸盐合成，表征以及催化性质

通过水热技术合成了两种新的Dowson结构硫钼多酸盐[C5N2H14]2[S2MoⅥ18O62].8H2O(1)和[C5N2H14]8(H3O)2[S2MoⅤ2MoⅥ16O62]3.(C5H5N)2(2),并通过X射线分析、红外光谱和元素分析其进行了表征。X射线晶体结果分析,化合物1结晶于正交晶系,Pmmn空间群,a=1.79929(17)nm,b=1.35804(13)nm,c=1.41926(13)nm,V=3.4680(6)nm3,Z=2。化合物2结晶于单斜晶系,C2/m空间群,a=2.266 5(3)nm,b=1.374 9(2)nm,c=3.291 2(5)nm,β=104.31(0)°,V=9.938(2)nm3,Z=4。化合物1和2都含有Dawson结构的硫钼多酸阴离子和质子化的N-甲基哌嗪阳离子。并且由苯乙烯的氧化催化结果中看出混价钼的化合物2的催化活性要比化合物1略高。     

Some aspects of the use of heteropoly anions in elemental analysis by simple potentiometric ion-pair formation-based titration

The possibility of the use of heteropoly anions formed by addition of phosphate to the solutions of either molybdate or tungstate in the determination of phosphorus by the simple method of potentiometric titration was studied. The heteropoly anions are titrated on the ion-pairing principle using a titrant containing a lipophilic counter-ion, i.e. 1-(ethoxycarbonyl)pentadecyltrimethylammonium bromide (Septonex), the titration being monitored by carbon paste electrode, although other liquid membrane-based electrodes can also be used. Calibration plots of the titrant end-point consumption vs. concentration are not linear, but allow one to evaluate the content of phosphorus. Similar procedures, when optimized, should be elaborated for determination of numerous other elements forming heteropoly anions.     

Ln[CrMo6O24H6]杂多配合物的合成与表征

合成了具有Anderson结构的Ln[CrMo6O24H6]（Ln^3 =La,Ce,Pr,Nd,Sm,Gd,Dy,Yb）的8种杂多配合物，此类配合物属Anderson结构B型，通过ICP和TG及元素组成分析，确定了配合物的组成，利用IR，UV，^95Mo-NMR,ESR,XRD等方法进行了表征，借助TG－DTA、不同温度下的IR和XRD以及水溶性实验研究了配合物热解性质，结果表明，配合物分解温度为350℃-400℃。     

Ruthenium complexes with heteropoly anion PW11O39 7− and their redox properties

A new heteropoly complex PW₁₁Ru^IV and complexes of Ru^II, Ru^III and Ru^V based thereon have been obtained. Using specrophotometry the states of Ru^III and Ru^IV complexes in solution, the pH range of their stability, and the interaction of PW₁₁Ru^IV with ClO₄ ^–,SO₄ ^2–, Cl^– ions have been studied. A conclusion has been thus made that the ruthenium ion in such a complex is not incorporated in the heteropolyanion lattice, but is attached only to its external oxygen atoms. Kinetics of oxidation of PW₁₁Ru^IV and PW₁₁Ru^III with potassium chlorate have been studied. The activation energy and pre-exponential factor have been found for the reaction. The possibility that ClO₄ ^– and ClO₃ ^– in aqueous solutions can be activated by PW₁₁Ru^II with the former and by PW₁₁Ru^III and PW₁₁Ru^IV with the latter has been demonstrated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1363–1369, August, 1993.The authors wish to thank I. L. Krayevskaya and V. M. Novopashina for X-ray fluorescence and ionic chromatographic analyses, respectively.