三缺位杂多阴离子PW_9(O_(34))~(9-) 的二苯基硅衍生物的合成和表征

以Na8 H[PW9O3 4 ]·nH2 O与Ph2 SiCl2 为原料于乙腈中合成了三缺位杂多阴离子的二苯基硅衍生物(TBA)3[α-A -PW9O3 4 (Ph2 Si)3 ](TBA为四丁基铵盐的缩写)(记为I),并由元素分析、红外光谱、紫外光谱对化合物进行了表征,结果表明,二苯基硅通过六个Si-O -W桥键填充到三缺位杂多阴离子的骨架上,形成了开环的饱和笼形结构.热分析结果表明,该化合物的热分解温度在 4 95.2℃左右     

α-和β-[SiW_9O_(37)M_3(H_2O)_3]~(7-)(M=A1~(3+),Ga~(3+),In~(3+))的合成和钨-183核磁共振研究

本文报道了α和β-[SiW_9O_(37)M_3(H_2O)_3]~((?))(M=Al~(3+),Ga~(3+),In~(3+))钾、铯盐的合成和性质。6种化合物的钨-183核磁共振谱都含有2个峰,相对强度为2∶1,表明其阴离子分别具有Aα和Aβ型Keggin结构,即3个MO_6八面体是角顶共用。     

三缺位杂多阴离子α-A-PW9O349-的甲基硅衍生物(TBA)3[α-A-PW9O34(CH3SiO)3(CH3Si)]的合成和晶体结构

杂多化合物SiW11O398-的有机硅衍生物早在1978年就由Knoth报道[1],后来又有人报道了α-PW11O397-和α-PW9MO2O397-的有机硅衍生物[2,3].该类衍生物在抗HIV-1方面有重要的用途[4,5],因而,近年来引起了人们极大的重视.1996年Thouvenot及其合作者研究了三缺位杂多阴离子与有机硅的反应,并在相转移条件下合成了一些杂多阴离子的有机硅衍生物[6～9],但到目前为止,有关杂多化合物的有机硅衍生物报道还很少,该类化合物的晶体结构报道更少.本文报道了化合物(TBA)3[α-A-PW9O34(CH3SiO)3(CH3Si)](1)(TBA为四丁基铵盐的缩写)的合成和晶体结构.     

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-)。     

区分α-,β-[Siw9M3(H2O)3O39]7-(M=Al3+,Ga3+)Keggin结构三取代杂多阴离子几何异构体新方法

Keggin结构三取代的杂多化合物,α-和β-[Siw9M3(H2O)3Ｏ39]7-是两种重要的几何异构体[1],它们在催化、高质子导体和抗病毒等方面有重要应用[2,3].本文实验采用相转移方法[4～9],首次研究了三取代Keggin系列杂多化合物在有机溶剂苯中不同的微观结晶形态.提出了以杂多阴离子在有机溶剂中的微观结晶形态差异,作为区分Keggin结构三取代杂多阴离子几何异构体的新方法,该项工作填补了多酸在有机溶剂中微观晶态学研究方面的空白.     

一个新的超大铈锑钨酸盐阴离子Ce_3Sb_4W_2O_8(H_2O)_(10)(SbW_9O_(33))_4~(19-)

合成了一超大铈锑钨酸盐[Ce3Sb4W2O8（H2O）10（SbW9O33）4]（NH4）19·48H2O,用X射线单晶衍射法及元素分析确定了其结构.其晶胞参数为:α=1.890 8（6）nm,b=2.003 2（14）nm,c=2.865 3（12）nm,α=86.95（6）°,β=75.68（3）°,γ=67.52（5）°,υ=9.706（9）nm3,空间群P1.在杂多阴离子Ce3Sb4W2O8（H2O）10（SbW9O33）419-中,四个β-B-（SbW9O33）9-是通过一个大的中心集团[Ce3Sb4W2O8（H2O）10]17+连接起来的,中心集团中含有两个桥连{WO2-（H2O）}基,三个Ce（Ⅲ）离子和一个{Sb4O4}基团.三个Ce（Ⅲ）离子的配位数均为9,Ce（1）和 Ce（3）的配位环境相同,但不同于Ce（2）的配位环境,四个{SbW9O33}中的三个参与了向 Ce（Ⅲ）的配位.两个{SbW9O33}中的四个氧,三个水分子中的三个氧,{Sb4O4}中的一个氧及一个桥连{WO2（H2O）}中的一个氧向Ce（1）[或Ce（3）]配位;两个{SbW9O33}中的四个氧,两个水分子中的两个氧,{Sb4O4}中的一个氧及两个桥连{WO2（H2O）}中的两个氧向Ce（2）配位.在{Sb4O4}中,四个Sb原子的中心构成了一四面体.该离子属Cs点群,Sb（5）,Sb（8）和Ce（2）所在的平面是其对称面.     

α-和β-Cs_4H_3[SiW_9O_(37)Cr_3(H_2O)_3]·xH_2O的合成及其催化PhIO环氧化烯烃的性质

本文报道了α-和β-[SiW_9O_(37)Cr_3(H_2O)_3]~(7-)杂多阴离子铯、钾盐的合成、表征及其催化亚碘酰苯环氧化烯烃的性质.元素分析、磁化率、红外光谱及FAB质谱等数据表明,该杂多阴离子为三取代的Keggin结构.α-和β-[siW_9O_(37)aCr_3(H_2O)_3]~(7-)具有催化PhIO环氧化反-二苯乙烯、环己烯和苯乙烯生成相应环氧化物的性质。     

新型层柱材料Zn2Al-SiW9M3的合成、表征及催化性能研究

杂多阴离子柱撑粘土是一类新型层柱催化材料.本文采用水热合成与离子交换方法首次将三取代Keggin结构杂多阴离子α-[SiW9O37M3(H2O)3]n-(简写为SiW9M3,M＝Mn2+,Cr3+,Ti3+,Fe3+)嵌入到Zn-Al型阴离子粘土层间,并通过XRD、IR、DTA和元素分析等手段对其结构进行了表征,考察了它们在顺丁烯二酸环氧化反应中的催化活性.     

新型层柱微孔材料──Ga-W9-Co3三取代柱撑ZnAl型阴离子粘土的合成、表征及催化研究

新型层柱微孔材料──Ｇａ－Ｗ_９－Ｃｏ_３三取代柱撑ＺｎＡｌ型阴离子粘土的合成、表征及催化研究张继余,余新武,张淑云,胡长文,梁兆君,王恩波（东北师范大学化学系,长春,１３００２４）关键词过渡金属,三取代,杂多阴离子,嵌入,阴离子粘土杂多化合物是具有优...     

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...     

α-和β-K6H[GeW9V3O40].xH2O的合成及其^5^1V和^1^8^3W核磁共振研究

本文报道了α-和β-K6H[GeW9V3O40].xH2O的合成及其^5^1V和^1^8^3W NMR研究。^5^1V NMR谱只有一个单峰, ^1^8^3W NMR谱中有两个峰, 相对强度为2:1, 其^2J~w~-~o~-~-~w偶合常数分别为19.35和16.73Hz, 表明其阴离子分别为A型α-和β-Keggin结构, 即三个VO6八面体是角顶共用。     

An unusual product of the reaction of 1-phenyl-3-(3,4-dimethoxyphenyl)-3-(2-oxocyclohexyl)-1-propanone with hydrogen sulfide and acids: 2α-phenyl-2,4-ortho-(14,15-dimethoxybenzo)-cis-1-thiadecalin

The reaction of 1-phenyl-3-(3,4-dimethoxyphenyl)-3-(2-oxocyclohexyl)-1-propanone with hydrogen sulfide and acids gives an intramolecular rearrangement product, 2-phenyl-2,4-ortho-(14,15-dimethoxybenzo)-cis-1-thiadecalin in addition to the usual products of disproportionation of intermediate 2-phenyl-4-(3,4-dimethoxyphenyl)-5,6-tetramethylene-4H-thiopyran, namely, 5,6-tetramethylenethiopyrilium salts and 2-phenyl-4-(3,4-dimethoxyphenyl)-cis-1-thiadecalin. The configurational and conformational assignments for the sulfides, their sulfoxides, and sulfones were made by ¹³C NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 199–205, February, 1986.     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions:[NH3(CH2)4NH3]6[Co4(HzO)2(B-α-GeW9034)2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate,[NH3(CH2)4NH3]6 [Co4(H2O)2(B-α-GeW9O34)2]·7H2O 1,was hydrothermally synthesized and characterized by IR spectra and single-crystal X-ray diffraction.The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system,space group P21/c with a=16.6073(6),b=15.3333(5),C=19.9869(7)(A),β=103.41(1)°,Mr=5481.38,V=4950.8(3)(A)3,Z=2,Dc=3.677 g/cm3,F(000)=4900,μ(MoKα)=22.165 mm-1,GOOF=1.005,the final R=0.0228 and wR=0.0527.The crystal structure indicates that the[Co4(H2O)2(B-α-GeW9O34)2]12-polyoxoanion contains two trivacant Keggin[B-α-GeW9O34]10-fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement(C2h symmetry)leading to a sandwich-type structure.     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions： [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate, [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O 1, was hydrothermaUy synthesized and characterized by IR spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system, space group P21/c with a = 16.6073（6）, b = 15.3333（5）, c = 19.9869（7） A, β = 103.41（1）°, Mr = 5481.38, V = 4950.8（3） A3, Z = 2, Dc = 3.677 g/cm^3, F（000） = 4900, μ（MoKa） = 22.165 mm^-1, GOOF = 1.005, the final R = 0.0228 and wR = 0.0527. The crystal structure indicates that the [Co4（H2O）2（B-α-GeW9O34）2]^12- polyoxoanion contains two trivacant Keggin [B-α-GeW9O34]^10- fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement （C2h symmetry） leading to a sandwich-type structure.     

D301R树脂对Keggin型铁取代杂多阴离子的吸附性能研究

详细研究了D301R弱碱性阴离子交换树脂对Keggin型铁取代杂多阴离子PW11O39Fe(III)(H2O)4－ (PW11Fe)的吸附作用, 考察了不同pH和温度对吸附量和吸附速率的影响, 测定了不同温度下吸附的动力学曲线和吸附等温线, 提出吸附动力学模型和计算了吸附的热力学函数, 结果表明, 在pH 2～8的范围内, PW11Fe的吸附量随溶液pH值的升高而增加, 随溶液温度的升高而降低; 吸附动力学符合表面过程控制的准二级反应模型, 其速率常数k2在298 K时为 9.33×10－4 g•mg－1•min－1, 并随温度的升高而减小. 吸附等温线符合Freundlich吸附模型, 吸附热约为40 kJ•mol－1, 因此, 吸附为物理吸附.     

Low-lying electronic states of M(3)O(9)(-) and M(3)O(9)(2-) (M = Mo, W)

Multiple low-lying electronic states of M(3)O(9)(-) and M(3)O(9)(2-) (M = Mo, W) arise from the occupation of the near-degenerate low-lying virtual orbitals in the neutral clusters. We used density functional theory (DFT) and coupled cluster theory (CCSD(T)) with correlation consistent basis sets to study the structures and energetics of the electronic states of these anions. The adiabatic and vertical electron detachment energies (ADEs and VDEs) of the anionic clusters were calculated with 27 exchange-correlation functionals including one local spin density approximation functional, 13 generalized gradient approximation (GGA) functionals, and 13 hybrid GGA functionals, as well as the CCSD(T) method. For M(3)O(9)(-), CCSD(T) and nearly all of the DFT exchange-correlation functionals studied predict the (2)A(1) state arising from the Jahn-Teller distortion due to singly occupying the degenerate e' orbital to be lower in energy than the (2)A(1)' state arising from singly occupying the nondegenerate a(1)' orbital. For W(3)O(9)(-), the (2)A(1) state was predicted to have essentially the same energy as the (2)A(1)' state at the CCSD(T) level with core-valence correlation corrections included and to be higher in energy or essentially isoenergetic with most DFT methods. The calculated VDEs from the CCSD(T) method are in reasonable agreement with the experimental values for both electronic states if estimates for the corrections due to basis set incompleteness are included. For M(3)O(9)(2-), the singlet state arising from doubly occupying the nondegenerate a(1)' orbital was predicted to be the most stable state for both M = Mo and W. However, whereas M(3)O(9)(2-) was predicted to be less stable than M(3)O(9)(-), W(3)O(9)(2-) was predicted to be more stable than W(3)O(9)(-).     

Structure and magnetism of the tetra-copper(II)-substituted heteropolyanion [Cu(4)K(2)(H(2)O)(8)(alpha-AsW(9)O(33))(2)](8-)

The novel heteropolyanion [Cu(4)K(2)(H(2)O)(8)(alpha-AsW(9)O(33))(2)](8)(-) (1) has been synthesized and characterized by IR spectroscopy, elemental analysis, and magnetic studies. Single-crystal X-ray analysis was carried out on [K(7)Na[Cu(4)K(2)(H(2)O)(6)(alpha-AsW(9)O(33))(2)].5.5H(2)O](n)(K(7)Na-1), which crystallizes in the tetragonal system, space group P42(1)m, with a = 16.705(4) A, b = 16.705(4) A, c = 13.956(5) A, and Z = 2. Interaction of the lacunary [alpha-AsW(9)O(33)](9)(-) with Cu(2+) ions in neutral, aqueous medium leads to the formation of the dimeric polyoxoanion 1 in high yield. Polyanion 1 consists of two alpha-AsW(9)O(33) units joined by a cyclic arrangement of four Cu(2+) and two K(+) ions, resulting in a structure with C(2)(v)() symmetry. All copper ions have one terminal water molecule, resulting in square-pyramidal coordination geometry. Three of the copper ions are adjacent to each other and connected via two micro(3)-oxo bridges. EPR studies on K(7)Na-1 and also on Na(9)[Cu(3)Na(3)(H(2)O)(9)(alpha-AsW(9)O(33))(2)].26H(2)O (Na(9)-2) over 2-300 K yielded g values that are consistent with a square-pyramidal coordination around the copper(II) ions in 1 and 2. No hyperfine structure was observed due to the presence of strong spin exchange, but fine structure was observed for the excited (S(T) = 3/2) state of Na(9)-2 and the ground state (S(T) = 1) of K(7)Na-1. The zero-field (D) parameters have also been determined for these states, constituting a rare case wherein one observes EPR from both the ground and the excited states. Magnetic susceptibility data show that Na(9)-2 has antiferromagnetically coupled Cu(2+) ions, with J = -1.36 +/- 0.01 cm(-)(1), while K(7)Na-1 has both ferromagnetically and antiferromagnetically coupled Cu(2+) ions (J(1) = 2.78 +/- 0.13 cm(-)(1), J(2) = -1.35 +/- 0.02 cm(-)(1), and J(3) = -2.24 +/- 0.06 cm(-)(1)), and the ground-state total spins are S(T) = 1/2 in Na(9)-2 and S(T) = 1 in K(7)Na-1.     

Synthesis and structure of the pentacopper(II) substituted tungstosilicate [Cu5(OH)4(H2O)2(A-alpha-SiW9O33)2]10-

The dimeric, pentacopper(II) substituted tungstosilicate [Cu(5)(OH)(4)(H(2)O)(2)(A-alpha-SiW(9)O(33))(2)](10-) (1) has been synthesized in good yield using a one-pot procedure by reaction of Cu(2+) ions with the trilacunary precursor salt K(10)[A-alpha-SiW(9)O(34)]. The title polyanion represents the first polyoxotungstate substituted by 5 copper centers and the central copper-hydroxo-aqua fragment is completely unprecedented. In the course of the reaction, two [A-alpha-SiW(9)O(34)](10-) Keggin half-units have fused in an asymmetrical fashion resulting in the lacunary polyoxotungstate [Si(2)W(18)O(66)](16-). The vacancy in this species is stabilized by a magnetic cluster of five octahedrally coordinated Cu(2+) ions resulting in polyanion 1 with C(2v) symmetry.