萘相吸光光度法研究

本文以萘作为固体萃取剂，以镍－丁二酮肟显色体系为例进行实验，探索出一种新的固相吸光光度法－萘相吸光光度法。镍在０－１００μｇ／５０ｍＬ范围内符合比耳定律，方法应用于水样中痕量镍的分析，结果良好。此种新的分析方法分离富集和显色测定两步相结合。灵敏度高，选择性好，快速简便，是一种很有发展前途的痕量元素分析方法。     

2-(2-喹啉偶氮)-5-二乙氨基苯甲酸固相萃取光度法测定环境水样中的镍

用2－（2－喹啉偶氮）－5－二乙氨基苯甲酸（QADEAB）与镍的显色反应及Waters Porapak^R Sep-Park固术萃取小柱对显色络合物的固相萃取，建立了测定水样中μg/L级镍的新方法。水样中的镍在pH=8.0的硼酸－磷酸二氢钾缓冲介质中和Tween 80存在下与QADEAB反应生成2：1稳定有色络合物，该络合物可用Waters Porapak^R Sep-Park固相萃取小柱富集，用乙醇洗脱后用光度法测定，可测定水样中μg/L级的镍。方法用于几种环境水样分析，结果令人满意。     

石蜡相光度法测定混合稀土中的铈

系统研究了Ｃｅ（Ⅳ）－８－羟基喹啉体系在石蜡相中的显色反应。在ＮＨ４Ｃｌ－ＮＨ３（ｐＨ＝９．５）介质中,Ｃｅ（Ⅳ）－８－羟基喹啉有色络合物可定量被石蜡萃取,且固相色阶明显,铈量在０～１００ｕｇ／５０ｍＬ范围内符合比耳定律,从而建立了测量铈的新的固相分光光度法。其它稀土离子的干扰可通过双波长光度法测量扣除。方法应用于混合稀土合成样中铈的测定,结果满意。     

镀锌镍铁合金溶液中硫酸镍的快速测定

镀锌镍铁合金溶液中硫酸镍的测定,过去采用了二酮肟镍重量法,过程冗长,分析费时。本文制定了丁二酮肟光度法,用于镀液中硫酸镍的快速测定。对于镍铁体系中镍的光度法测定,过去采用酒石酸钾钠掩蔽铁,但酒石酸铁络合物的颜色与丁二酮肟镍相近,影响镍的测定。本文选用三乙醇胺掩蔽铁,使铁在碱性溶液中生成无色络合物,有效地消除了铁对测定镍的影响。以往的经验认为,丁二酮肟与镍离子的显色速度     

蜡相分光光度法研究（Ⅰ）—镍的测定

以镍（Ⅱ）－丁二酮肟－石蜡体系为对象，提出一种新的固相（蜡相）分光光度法，并研究了方法的最佳实验条件；镍量在０～３０μｇ／５０ｍＬ范围内服从比尔定律。本法将显色、富集、分离、测定结合起来，选择性好、灵敏度高。应用于工业废水中镍的测定，结果满意。     

对偶氮苯重氮氨基偶氮苯磺酸分光光度法测定水和土壤中的痕量镍

在ＴｒｉｔｏｎＸ－１００和四硼酸钠介质中，题示试剂与镍产生灵敏的显色反应，所生成的紫红色络合物最大吸收波长５４６ｎｍ，摩尔吸光系数为２．３×１０＾５Ｌ．ｍｏｌ＾－＾１．ｃｍ＾－＾１，镍在０－１２μｇ／２５ｍｌ范围内遵守比耳定律。干扰离子可用丁二酮肟－正丁醇萃取法消除。拟定的方法应用于水样和土壤样品中镍的测定。结果满意。对水样２＾＃和土壤样５＾＃６次测定的相对标准偏差分别为６．２％和４．９％。     

微晶萘相光度法测定镍的研究

本文试验研究确定了微晶萘Ni(Ⅱ)-丁二酮肟显色体系测定方法的最佳试验条件。该方法是将固态萃取法分离出的吸萃了Ni(Ⅱ)-丁二酮肟络合物的微晶萘,经过滤、洗涤、自然干燥后,移人比色皿中测其吸光度。结果表明,该方法具有选择性好、萃     

2—[2‘—苯并噻唑偶氮]—1,8—二羟基萘—3,6—二磺酸的合成及与铝的显…

本合成了新的显色试剂２－［２＇－苯并噻唑偶氮］－１，８－二羟基萘－３，６－二磺酸，并研究了与铝的显色反应，在ＣＴＭＡＢ存在下，铝与试剂于ＰＨ７．０－８．０的缓冲溶液中的形成稳定的深紫红色络合物，组成为Ａｌ（Ⅲ）：Ｒ＝１：２，表观摩尔吸光系数为１．４６×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，铝浓度在０－５．０μｇ／２５ｍＬ范围内符合比尔定律。     

丁二酮肟作为镍离子的光度显色剂的基本原理是什么？

福建读者———丁萍答 :当有氧化剂存在时丁二酮肟与镍离子形成水溶性络合物。关于这一显色反应的机理 ,在近年的报道中趋向于认为二价镍离子在氨性或碱性溶液中先被氧化剂 (如溴、碘、过硫酸铵、过氧化氢等 )氧化为四价 ,然后与丁二酮肟 (H2 DX)形成络合物。随溶液介质及碱度的不同 ,络合物分子的组成比Ni∶H2 DX可能为 1∶2 ,1∶3或 1∶4。在pH≤ 11.5的氨性溶液中主要形成 1∶2络合物 (λmax=4 40nm ,ε =1.6×10 4 L·mol- 1·cm- 1) ,而在pH≥ 12的氢氧化钠溶液中主要形成 1∶ 4的络合物 (λmax =4 6 5nm)。有研究证实镍 (Ⅳ )与H…     

4,5—二溴苯基荧光酮光度法测定钇

研究４，５－二溴苯基荧光酮灵敏光度法测定钇。在ｐＨ５．５缓冲溶液中钇与ＤＢＰＥ形成橙红色络合物，最大吸收波长位于５５０ｎｍ，表观摩吸光系ε值１．５３×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，钇量在每２５ｍＬ０－８μｈ范围内服从比耳定律，测定极限６．８μｇ／Ｌ，对于钇０．２４ｍｇ／Ｌ测定的相对标准偏差为２．６％，络合物的摩尔组成为Ｙ：ＤＢＰＦ＝１：３。方法用于镁合金和地质标样中钇的测定，结果满意。     

New Cd(II)-, Co(II)-, and Cu(II)-containing coordination polymers synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA)

Four new organic/inorganic coordination polymers, [Cd(C(10)H(8)N(2))(2)(H(2)O)(2)(NO(3))(2)](n)(1), [Co(C(10)H(8)N(2))(H(2)O)NO(3)CH(3)OH](n)(2), [Cu(C(10)H(8)N(2))(CH(3)OH)(NO(3))(2)](n) (3), and [Cu(C(10)H(8)N(2))(hfac)(2)](n)(4), were synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA). Complex 1 crystallizes in space group P2/n: a = 12.462(2) A, b = 9.485(1) A, c = 13.383(2) A, beta = 96.629(2) degrees, V = 1559.6(3) A(3), Z = 4. Complex 2 crystallizes in space group Fddd: a = 9.248(4) A, b = 19.982(7) A, c = 35.093(16) A, V = 6485.0(4) A(3), Z = 8. Complex 3 crystallizes in space group I2/a: a = 18.315(2) A, b = 8.517(1) A, c = 20.494(3) A, beta = 104.042(2) degrees, V = 3101.2(7) A(3), Z = 8. Complex 4 crystallizes in space group P21/c: a = 6.576(1) A, b = 16.189(1) A, c = 11.653(1) A, beta = 91.337(1) degrees, V = 1240.3(2) A(3), Z = 2. The coordination polymers display a variety of structural architectures, ranging from sinusoidal and zigzag chains (1, 3, 4) to two-dimensional channel-type architectures (2). The effects of the orientation of the nitrogen atom in the pyridine rings on the resultant structures are discussed.     

Cationic and neutral diphenyldiazomethanerhodium(I) complexes as catalytically active species in the C-C coupling reaction of olefins and diphenyldiazomethane

Cationic rhodium(I) complexes cis-[Rh(acetone)2(L)(L')]+ (2: L = L'=C8H14; 3: L=C8H14; L'=PiPr3; 4: L=L'=PiPr3), prepared from [RhCl(C8H14)2]2] and isolated as PF6 salts, catalyze the C-C coupling reaction of diphenyldiazomethane with ethene, propene, and styrene. In most cases, a mixture of isomeric olefins and cyclopropanes were obtained which are formally built up by one equivalent of RCH=CH2 (R = H, Me, Ph) and one equivalent of CPh2. The efficiency and selectivity of the catalyst depends significantly on the coordination sphere around the rhodium(I) center. Treatment of 4 with Ph2CN2 in the molar ratio of 1:1 and 1:2 gave the complexes trans-[Rh(PiPr3)2(acetone)(eta1-N2CPh2)]PF6 (8) and trans-[Rh(PiPr3)2(eta1-N2CPh2)2]PF6 (9), of which 8 was characterized by X-ray crystallography. Since 8 and 9 not only react with ethene but also catalyze the reaction of C2H4 and free Ph2CN2, they can be regarded as intermediates (possibly resting states) in the C-C coupling process. The lability of 8 and 9 is illustrated by the reactions with pyridine and NaX (X=Cl, Br, I, N3) which afford the mono(diphenyldiazomethane)rhodium(I) compounds trans-[Rh(PiPr3)2(py)(eta1-N2CPh2)]PF6 (10) and trans-[RhX(eta1-N2CPh2)(PiPr3)2] (11-14), respectively. The catalytic activity of the neutral complexes 11 - 14 is somewhat less than that of the cationic species 8, 9 and decreases in the order Cl > Br> I > N3.     

两个新型三核镍(Ⅱ)配合物的合成及其晶体结构

5-溴水杨醛和5-氯水杨醛分别与N-环己基-1,2-丙二胺经缩合反应制得Schiff碱配体(L1和L2); L1和L2分别与Ni(Ac)₂·4H₂O经配位反应合成两个新型的三核Schiff碱配合物(1和2),其结构经X-射线单晶衍射表征。1(CCDC: 1 008 203)和2(CCDC: 1 008 204)属单斜晶系,空间群P2₁/c,晶胞参数1：a=9.111(4) , b=12.089(6) , c=18.724(8) , β=92.117(7)°; 2： a=9.346 8(12) , b=11.507 3(15) , c=18.539(2) , β=93.774(2)°。     

烯唑醇锌盐配合物的合成与结构表征

合成了 2个新配合物ZnL4 Cl2 和ZnL4 (H2 O) 2 ·(NO3 ) 2 (L =烯唑醇 ) ,通过元素分析、IR光谱和核磁共振谱表征了配合物的结构 .X射线单晶衍射结构分析表明 :ZnL4 Cl2 晶体属三斜晶系 ,空间群P墿,晶胞参数 :a =0 882 80(7)nm ,b =1 370 94(11)nm ,c=1.5 182 9(13)nm ,α =91.0 72 (10 )°,β =98 5 97(10 )°,γ =10 6 .779(8)° ,V =1.735 8(2 )nm3 ,Z =1;ZnL4 (H2 O) 2 ·(NO3 ) 2 晶体属单斜晶系 ,空间群Cc,晶胞参数 :a =1.5 2 430 (13)nm ,b =1.5 85 4(2 )nm ,c =3.336 1(4 )nm ,α =90 0 0 0° ,β =10 0 .2 2 7(8)° ,γ =90 0 0 0°,V =7 934 (2 )nm3 ,Z =1     

Methylaluminium 8-quinolinolates: synthesis, characterization and use in ring-opening polymerization (ROP) of ε-caprolactone

The stoichiometric reactions of 2-(2,6-R-phenylimino)quinolin-8-ol (L1-L5, L1: R = Me, L2: R = Et, L3: R = (i)Pr, L4: R = Cl, L5: R = F) with Me(3)Al afforded the dimeric aluminium complexes [Me(2)AlL](2) (1-5) in good yields. By contrast, stoichiometric reactions of 2-(1-(2,6-R-phenylimino)propyl) quinolin-8-ol (L6-L10, L6: R = Me, L7: R = Et, L8: R = (i)Pr, L9: R = Cl, L10: R = F)) with Me(3)Al gave the mononuclear aluminium complexes Me(2)AlL (6-10) accompanied with by-products of the form Me(2)AlL·Me(3)Al (11-15). All methylaluminium complexes were characterized by NMR spectroscopy, elemental analysis, and the molecular structures of complexes 3, 6 and 8 were determined by single-crystal X-ray diffraction. Aluminium compounds 1-5 possessed negligible activity towards the ring-opening polymerization of ε-caprolactone either in the presence or absence of BnOH. In contrast, in the presence of BnOH, the mononuclear aluminium compounds 6-10 could efficiently initiate the ring-opening polymerization of ε-caprolactone; the polymerization proceeded in a living manner.     

The pi complexation of alkali and alkaline earth ions by the use of meso-octaalkylporphyrinogen and aromatic hydrocarbons

The full metallation of meso-octaalkylporphyrinogens [R8N4H4] (R=Et, 1; nBu, 2; CH2Ph, 3; (CH2)4, 4) with heavy alkali metals (M = K, Rb, Cs) leads to the porphyrinogen-M4 compounds, in which the solvation of the alkali cations is largely assured by the intra- and intermolecular phi-interactions with the pyrrolyl anions. Such a mode of complexation results in a structural diversity as a function of the meso substituents, the size of the metal ion, and the solvent. The structure of the unsolvated polymers [R8N4M4]n (R= Et, M=K, 5; M=Rb, 6; M=Cs, 7; R= (CH2)4, M = Rb, 8; M = Cs, 9) have been clarified through the X-ray analysis of 7 recrystallized from diglyme. The structure shows that the tetraanion binds two Cs ions inside the cavity, which display in one case eta1:eta1:eta1:eta1 and in the other eta5:eta5:eta5:eta5 interaction modes. Bidimensional polymerization is assured by four Cs ions, which each bind at the eta5 position on the exo face of each pyrrole. With bulkier meso substituents, different polymeric forms are obtained (R = nBu, M = K, 10; M = Rb, 11; M = Cs, 12), and their structures were clarified through the X-ray analysis of 10, which was recrystallized from dimethoxyethane. The polymeric units are made up by the monomeric units [Bu8N4K2]2-, in which one potassium is eta1:eta1:eta1:eta5 and the other eta5:eta1:eta5:eta1 bonded inside the porphyrinogen cavity. In the case of R=CH2Ph, the monomeric anion [(PhCH2)8N4K2]2- (13) has been structurally identified. The metallation of 1 and 2 with active forms of alkaline earth metals (M' = Ca, Sr, Ba) led to dinuclear compounds [R,N4M'2] (R = Et, M' = Ca, 14; M'=Sr, 15; M'=Ba, 16; R=nBu. M'=Ba, 18), in which both metals inside the cavity are eta1:eta3:eta1:eta3 (Ca) and eta1:eta5:eta1:eta5 (Sr and Ba) bonded to the porphyrinogen tetraanion. The coordination sphere of each metal ion is completed by two THF molecules, which, in the case of Ba, are easily replaced by an arene ring [Bu8N4Ba2(eta6-arene)2] (arene=durene, 22; naphthalene, 23; toluene, 24; benzene, 25). The X-ray structures of 14, 15, 18, 22, and 23 are described in detail. We have tried to establish a relationship between the solid-state and solution structures by analyzing the 1H NMR spectra of the porphyrinogen complexes.     

Unusual ligand coordination for cesium

When complexed by tetrabenzo-24-crown-8, the cesium ion can accommodate unprecedented ligation. The structures of the following complexes are presented. [Cs(tetrabenzo-24-crown-8)(eta 1-NCMe)2(eta 2-NCMe)][NO3] (1): triclinic P1, a = 12.0119(14) A, b = 13.3680(15) A, c = 13.7859(12) A, alpha = 89.124(8) degrees, beta = 66.928(9) degrees, gamma = 71.536(10) degrees, V = 1916.7(4) A3, Z = 2. [Cs(tetrabenzo-24-crown-8)(eta 1-NCMe)2(eta 2-CH2Cl2)][NO3] (2): triclinic, P1, a = 12.295(3) A, b = 13.295(3) A, c = 13.782(3) A, alpha = 89.105(17) degrees, beta = 66.096(18) degrees, gamma = 71.980(19) degrees, V = 1929.5(8) A3, Z = 2. These structures are the first reported examples of linear eta 2-acetonitrile coordination to any metal ion and the first structures illustrating eta 2-acetonitrile and dichloromethane ligation to an alkali metal ion. Possible steric and electronic origins of these unusual metal-ligand interactions are discussed.     

Syntheses and Crystal Structures of two Ring—like {Mo18}Cluster Compounds

1INTRODUCTIONThepolyoxomolybdateshavebeenwidelyresearchedinmanyfieldssuchascatalysis,biology,medicineandmaterialsciencebecauseoftheirrichphysicalandchemicalproperties[1].Thoughmanypolyoxomolybdateshavebeenreported[2],furtherresearchisstillnecessaryforthestudyof搑eduction-oxidation-reconstitution?self-assemblyprocesses[3,4].Polyoxomolybdatesarenormallybuiltupundersuitableconditionsbyafewbuildingblockssuchas{Mo2},{Mo8}and{Mo9}inself-assemblyway[5,6].The{Mo18}clustershaveseveralstructuralty…     

Tetrafluoroaurate(III) der Lanthaniden MF[AuF4]2 (M = Tm,Yb, Lu)

Tetrafluoroaurates(III) of Lanthanides MF[AuF₄]₂ (M = Tm, Yb, Lu) . Tetrafluoroaurates(III) MF[AuF₄]₂ with M = Tm, Yb, Lu, all yellow, have been prepared for the first time. From single crystal data they crystallize orthorhombic, space group Pbcn-D (No. 60) with M = Tm: a = 1 102.92(8) pm, b = 904.38(8) pm, c = 2 164.46(23) pm; M = Yb: a = 1 100.98(12) pm, b = 902.23(8) pm, c = 2 157.36(23) pm; M = Lu: a = 1 099.28(18) pm, b = 900.70(15) pm, c = 2 151.50(46) pm.     

一种新的三维超分子化合物[Ni(H2O)6(fum)]·2(hmt)·4H2O的合成和晶体结构(fum=反丁烯二酸根；hmt=六次甲基四胺)

The synthesis of nickel supramolecular compound with hexamethylenetetramine and fumarate ligands is reported. The compound [Ni(H₂O)₆(fum)]·2(hmt)·4H₂O (1) (fum=fumarate; hmt=hexamethylenetetramine) were characterized by elemental analysis, crystal structure, IR. Compound 1 crystallizes in the triclinic system, space group P1, and with Z=1. Cell parameters: a=0. 934 6(1), b=0.933 8(1), c=0.938 8(2) nm, α=79.46(1)°, β=77.84(1)°, γ=61.29 6(7)°. Every metal ion has a octahedral coordination geometry formed by six oxygen atoms from six water molecules, and the relative independent components [Ni(H₂O)₆]²⁺, fumarate anions, hmt and H₂O molecules are linked together by two kinds of hydrogen bonds (O-H…O, and O-H…N) to form a three-dimensional structure. CCDC: 256355.