THE RETENTION BEHAVIOR OF ARSENIC COMPOUNDS ON PRP-X100 COLUMN UNDER ALKALINE CONDITION

系统地研究了碱性条件下（ｐＨ８～１０．８）Ａｓ３＋，Ａｓ５＋，ＭＡ，ＤＭＡ和ＡＢ等砷化合物在ＰＲＰ－Ｘ１００阴离子交换柱上的保留行为。用火焰原子吸收光谱（ＦＡＡＳ）测定从ＨＰＬＣ分离的砷化合物，即通过一根１ｍ×０．２３ｍｍｉ．ｄ．不锈钢毛细管，将ＨＰＬＣ柱出口与ＦＡＡＳ的雾化器连接起来，采用乙炔／空气火焰，在１９３．７ｎｍ处测定。具体研究了两个流动相（２０ｍｍｏｌ／ＬＮＨ４ＨＣＯ３和２．５ｍｍｏｌ／Ｌ对－羟基苯甲酸－１．０ｍｍｏｌ／Ｌ苯甲酸水溶液），并系统研究了ｐＨ值和缓冲液浓度对上述５个砷化合物的保留时间的影响，发现对于２０ｍｍｏｌ／ＬＮＨ４ＨＣＯ３体系，在ｐＨ８．７时，ＡＢ，Ａｓ３＋，ＤＭＡ可以得到完全分离，通过梯度洗提（ｐＨ８．７到９．８，流速１．６５ｍＬ／ｍｉｎ），在１５ｍｉｎ内上述５个砷化合物可以得到良好分离；对于２．５ｍｍｏｌ／Ｌ对－羟基苯甲酸－１．０ｍｍｏｌ／Ｌ苯甲酸体系，在ｐＨ９．０及流速１．５ｍＬ／ｍｉｎ时，可以在１２ｍｉｎ内将上述５个砷化合物分离。     

偏最小二乘催化极谱法同时测定铂,钯,铑

应用Ｍ２７３Ａ电化学系统中的线性扫描技术，确定了０．７５ｍｏｌ／ＬＨ２ＳＯ４－１．５％ＮＨ４Ｃｌ－２．８ｍｍｏｌ／Ｌ（ＣＨ２）６Ｎ４－０．００２５％Ｎ２Ｈ４．Ｈ２ＳＯ４为偏最小二乘极谱法同时测定Ｐｔ、Ｐｄ、Ｒｈ的最佳极谱体系。Ｐｔ、Ｐｄ、Ｒｈ的线性范围为３．２ｍｇ／Ｌ、０－１５．０ｍｇ／Ｌ和０－１．０ｍｇ／Ｌ。模拟样品及实际样品的回收率在９０．３－１０７．７％之间。     

秋水仙碱在碳糊电极上的吸附伏安行为

秋水仙碱在硫酸溶液中加热水解得分析试液。在０．０５ｍｏｌ／ＬＨ２ＳＯ４底液中，用碳糊电极吸附伏安法测定秋水仙碱，阳性峰电位为０．８２Ｖ（ｖｓ．ＳＣＥ），峰电流与秋水仙碱的浓度在１．０×１０＾－７～１．０×１０＾－４ｍｏｌ／Ｌ范围内呈良好线性关系，检测下限为５．０×１０＾－８ｍｏｌ／Ｌ回收范围为９５．０％～１０３．５％ＲＳＤ为２．８％（ｎ＝１０）。本对反应机理进行了初步探讨。     

磷酸三丁酯增敏极谱法测定铜的研究

在０．００４ｍｏｌ／Ｌ ＨＣｌ－１×１０＾－３ｍｏｌ／Ｌ ＳＣＮ＾－－５×１０＾－５ｍｏｌ／Ｌ磷酸三丁酯（ＴＢＰ）溶液中，Ｃｕ＾２＋可在－０．４２Ｖ（ｖｓ．ＳＣＥ）产生灵敏的极谱波，波高较无ＴＢＰ存在时增加近３倍，二阶导数峰电流与０．００５￣４．０ｍｇ／Ｌ Ｃｕ＾２＋呈线性关系。研究了极谱波性质及增敏机理，表明该极谱波为配合物吸附波，ＴＢＰ起协同吸附作用。本法已用于实际样品分析，结果满意。     

丁基罗丹明B-铜钨杂多酸光度法测定微量铜

在聚乙烯醇（ＰＶＡ）存在下，丁基罗丹明Ｂ（ＢＲＢ）与铜钨杂多酸形成离子缔合物。缔合物的形成条件为ｃＨ２ＳＯ４＝１．２ｍｏｌ／Ｌ，ｃＷＯ２－４＝６．１×１０－５ｍｏｌ／Ｌ，ｃＢＲＢ＝３．８×１０－５ｍｏｌ／Ｌ和ＰＶＡ０．０８％。缔合物的最大吸收波长位于５７０ｎｍ，摩尔吸光系数ε＝１．６６×１０６Ｌ·ｍｏｌ－１·ｃｍ－１，铜量在每２５ｍＬ０～０．５μｇ范围内服从比耳定律，检测限为每ｍＬ０．６５ｎｇ（ｎ＝１２），对每ｍＬ１８ｎｇＣｕ测定的ＲＳＤ为０．８５％（ｎ＝１０）。缔合物至少稳定１５０ｈ，其摩尔比为Ｃｕ∶Ｗ∶ＢＲＢ＝１∶１２∶５，红外图谱表明铜钨杂多酸具有Ｋｅｇｇｉｎ结构。考察了４０多种共存离子的影响，大多数常见元素不干扰。本法已用于天然水、自来水、降水、人发、中药和蔬菜中铜的测定，结果满意。     

反相离子对色谱法测定硫代硫酸根和碘离子的研究

首次利用Ｓ２Ｏ２－３和Ｉ－与Ｈｇ－ＥＤＴＡ二元络合物通过柱前衍生形成ＥＤＴＡ－Ｈｇ－Ｓ２Ｏ３和ＥＤＴＡ－Ｈｇ－Ｉ两种三元络合物的方法,实现了对Ｓ２Ｏ２－３和Ｉ－的间接反相离子对色谱分离和紫外检测。在ＺｏｒｂａｘＯＤＳ柱上,用甲醇∶水＝２３∶７７作流动相,内含对离子ＴＢＡ＋３．０ｍｍｏｌ／Ｌ,ＥＤＴＡ１．０ｍｍｏｌ／Ｌ,ＮａＮＯ３２．０ｍｍｏｌ／Ｌ和缓冲剂ＫＨ２ＰＯ４－Ｎａ２ＨＰＯ４（ｐＨ７．０）,紫外２５４ｎｍ检测。Ｓ２Ｏ２－３和Ｉ－的最小检出限分别为６１．１ｎｇ和３７．６ｎｇ。方法简便,选择性好。     

酸性媒染紫-示波计时电位法测定天然水和饮用水中铝

报道酸性媒染紫（ＳＶＲＳ）－示波计时电位法测定天然水及饮用水中铝。在０．８５ｍｏｌ／Ｌ　ＮＨ３·Ｈ２Ｏ－ＮＨ４Ｃｌ－５×１０－５ｍｏｌ／Ｌ ＳＶＢＳ（ｐＨ８．８）底液中,Ａｌ－ＳＶＲＳ络合物在－１．０５Ｖ电位处产生灵敏切口,切口深度与铝浓度成正比,可用于定量分析。线性范围为１×１０－７～６×１０－６ｍｏｌ／Ｌ． ＲＳＤ为５．５％ （ｎ＝１０,２×１０－７ｍｏｌ／Ｌ）,检测限为５×１０－８ｍｏｌ／Ｌ。本法特点为：在碱性条件下,无需加热,无需通氮除氧,无需预富集,大大减少了分析时间。仪器简单,方法灵敏准确,特别适用于天然水和饮料中Ａｌ的分析。对实际水样进行了分析,与ＩＣＰ／ＡＥＳ法所测结果基本一致。     

The retention behavior of arsenic compounds on PRP-X100 column under alkaline condition.

系统地研究了碱性条件下（ｐＨ８～１０．８）Ａｓ３＋,Ａｓ５＋,ＭＡ,ＤＭＡ和ＡＢ等砷化合物在ＰＲＰ－Ｘ１００阴离子交换柱上的保留行为。用火焰原子吸收光谱（ＦＡＡＳ）测定从ＨＰＬＣ分离的砷化合物,即通过一根１ｍ×０．２３ｍｍｉ．ｄ．不锈钢毛细管,将ＨＰＬＣ柱出口与ＦＡＡＳ的雾化器连接起来,采用乙炔／空气火焰,在１９３．７ｎｍ处测定。具体研究了两个流动相（２０ｍｍｏｌ／ＬＮＨ４ＨＣＯ３和２．５ｍｍｏｌ／Ｌ对－羟基苯甲酸－１．０ｍｍｏｌ／Ｌ苯甲酸水溶液）。     

头孢哌酮钠的伏发行为及其应用研究

头孢哌酮钠在０．０５ｍｏｌ／Ｌ Ｈ２ＳＯ４溶液中,形成一良好的示波极谱导数峰。峰电位为－０．８２Ｖ（ｖｓ．ＳＣＥ）。峰电流与头孢哌酮钠的浓度在１．０×１０＾－７－２．０×１０＾６ｍｏｌ／Ｌ范围内成线性关系。检出限为５．０×１０＾－８ｍｏｌ／Ｌ。回收率在９４．０％－１０２．０％之间。并用于尿样的测定,得到满意的结果。     

6－硝基喹啉的单扫示波极谱分析

研究了６－硝基喹啉在滴汞电极上的电极过程并建立了它的单扫示波极谱测定法。在０．１０ｍｏｌ／ＬＮａＣｌ底液中，６－硝基喹啉的二阶导数阴极波峰电流ｉ”ｐ（Ｅ”ｐ＝－０．６６ＶｖｓＳＣＥ）与浓度在１．０×１０－７～２．５×１０－５ｍｏｌ／Ｌ范围内有良好线性关系，检出限为４．２×１０－８ｍｏｌ／Ｌ，ＲＳＤ＝１．７％（ｎ＝６）。此外还考察了多种人体内常见微量物质及表面活性剂对ｉ”ｐ的影响。     

X-ray crystal structure of (eta(5)-pentaphenylcyclopentadienyl)[1-(eta(5/6)-phenyl)-2,3,4,5-tetraphenylcyclopentadienyl]iron(II), [Fe(eta(5)-C(5)Ph(5))[(eta(5/6)-C(6)H(5))C(5)Ph(4)]], a linkage isomer of decaphenylferrocene

Very dark blue prismatic crystals of [Fe(eta(5)-C(5)Ph(5))[(eta(5/6)-C(6)H(5))(C(5)Ph(4))]], the linkage isomer of decaphenylferrocene, were grown from (3:1 v/v) hexane/ethyl acetate and characterized by single-crystal X-ray diffraction (space group P2(1)/n, R1(F) 0.0404). The iron atom is coordinated to two C(5)Ph(5) ligands: one with an eta(5)-C(5)-configuration and the other with a coordinated arene configuration. The phenyl groups of the (eta(5)-C(5)Ph(5)) ligand are oriented in a "paddle-wheel" arrangement about the C(5) ring, with which four of them make an average angle of approximately 53 degrees, the other, an angle of approximately 42 degrees. The coordinated C(6)H(5) ring of the other ligand is inclined at only approximately 5 degrees to the uncoordinated C(5) ring, with which three of the other four phenyl rings make an average angle of approximately 64 degrees, and the other (opposite the coordinated arene ring), an angle of 38 degrees.     

Distortions in trihapto-allyls induced by electronic asymmetry: A comparison of the structures of (η5-C5H5)Mo(CO)2(η3-C3H5) and (η5-C5H5)Mo(NO(I)(η3-C3H5)

The electronic asymmetry induced by replacing two carbonyls by a nitrosyl and iodide ligand causes severe distortion in the allyl moiety. The allyl group in the nitrosyl complex is bound in a sigma-pi mode rather than the symmetrical mode found in the dicarbonyl. This change in ground state structure alters the exo—endo conformer interconversion mechanism from a rotation of the allyl in the dicarbonyl to a sigma-pi interconversion in the nitrosyl iodide.     

Molekülsruktur und abs. konfiguration von (+)-p-menthadien-(1,8)-on-(2)-rhodium(I)-h5-cyclopentadienid, (+)-(4S-Carvon) RhI(C5H5)

The title compound crystallizes in the orthorhombic space group P2₁2₁2₁ with 4 molecules in the unit cell (cell dimensions: a 9.778(2), b 10.639(2) and c 12.423(4) Å). The structure was solved by means of the heavy atom method. The rhodium atom is linked to both olefinic double bonds. The terpene carbonyl group does not participate in coordination to rhodium. Unlike the endocyclic olefinic group, which is approximately perpendicular to the coordination plane of rhodium, the exocyclic Cz.sbnd;C double bound shows a considerable deviation from this arrangement. The π-complexation of carvone with rhodium proceeds diastereospecifically. The absolute configuration of (+)-carvone is 4S in agreement with the assignment derived by indirect chemical correlation.     

钼铁混合金属原子簇化合物[(η5-C5H5)4Mo4Fe2(μ3-S)5(CO)5]的合成和结构

(η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5 have been prepared from (η~5-C_5H_5)_2Mo_2(CO)_6 and Fe_8S_2(CO)_9 under toluene reflux for 14.5 hrs.The crystal and molecular structures of (η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5 were studied by X-ray structure analysis. The Crystallographic data are as follows: monoclinic, space group P2_1/n, unit cell: a=1.0589(4), b=1.7260(4), c=1.8963(4) nm, β=101.44(2)°, V=3.3967 nm, D_c=2.06 gcm~(-3) for Z=4, X-ray data were obtained over the range of 2°<2θ<50° via the ω-2θ scan mode with MoKα radiation on an Enraf-Nonius CAD4 diffractometer. The structure was solved by direct method (MULTAN) and refined by full matrix least-squares techniques for 3993 reflections with I>2σ(I), The final R=0.081. Figure 1 illustrates the configuration of the molecule (η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5, composing of a cubane-like (FeMo_3S_4) core and a trigonal pyramid (MoFe_2S) core, which linked by sharing Fe(1) atom.     

Mechanism of the thermal decomposition of (η5-C5H5)Fe(CO)2(η1-acenaphthenyl)

The complexes (η⁵-C₅H₅)Fe(CO)₂(η¹-acenaphthenyl) (I), (η⁵-C₅H₅)Fe(CO)₂ (η¹-trans-β-deuterioacenaphthenyl) (II), and (η-C₅D₅)Fe(CO)₂, (η¹-acenaphthenyl) (XIII) have been prepared and their thermal decomposition studied in vacuo and in refluxing toluene. All three complexes decompose to produce mixtures of acenaphthene (VII), acenaphthylene (VIII), and [C₅H₅Fe(CO)₂]₂ (VI). Biacenaphthenyl (IX) is also obtained from the thermolysis of I in toluene. The formation of alkene VIII, and, to a lesser extent, alkane VII is suppressed by external CO. Thermolysis of I in toluene-d₈ and of II in vacuo and in toluene produces deuterium-enriched VII. The acenaphthene generated from the decomposition of XIII also contains deuterium. The above observations are accomodated by a mechanistic scheme involving competing β-elimination, ironcarbon bond homolysis to produce the acenaphthenyl radical, and CpH abstraction by an undetermined pathway.     

Unsymmetrische(Rh—Rh)-zweikernkomplexe mit 34 valenzelektronen: Synthese und eigenschaften von C5Me5(L)Rh(μ-CO)2RhC5Me5

[C₅Me₅Rh(μ-co)]₂ reacts with phosphines (PMe₂H, PMe₃) and trimethylphosphite to give the binuclear complexes C₅Me₅(L)Rh(μ-CO)₂RhC₅Me₅ which have been characterised by elemental analyses, mass spectra,¹H and ³¹P NMR data. They are surprisingly inert toward an excess of L and do not react to give the mononuclear compounds C₅Me₅Rh(CO)L. These are obtained in good yields from C₅Me₅Rh(CO)₂ and L where L is PMe₂H, P(OMe)₃, PEt₃, P(OEt)₃ and PMe₂Ph.     

Antimonypentafluoroorthotellurates: Sb(OTeF5)3, Sb(OTeF5)5 and salts of Sb(OTeF5)6−

Antimony(III)pentafluoroorthotellurate has been synthesized from SbF₃ and B(OTeF₅)₃. Contrary to a previous report it is a low melting, sublimable solid (mp = 28°, bp (0.1 torr) = 68°, ¹⁹F - NMR: AB₄ spinsystem δ (A) = ?42.7, δ (B) = ?38.1, J (AB) = 186 Hz). It reacts with F₂, Cl₂ and Br₂ to give SbF₂(OTeF₅)₃, SbCl₄⁺Sb(OTeF₅)₆^? and SbBr₄⁺ Sb(OTeF₅)₆^? respectively. Interaction of Xe(OTeF₅)₂ and Sb(OTeF₅)₃ yields Sb(OTeF₅)₅, which is unstable at room temperature. Salts containing the new anion Sb(OTeF₅)₆^? have been synthesized either from Sb(OTeF₅)₅ and a corresponding pentafluoroorthotellurate e.g. Sb(OTeF₅)₅ + NMe₄⁺ OTeF₅^? = NMe₄⁺ Sb(OTeF₅)₆^?, or from SbCl₄ Sb(OTeF₅)₆^? and an appropriate chloride SbCl₄⁺ Sb(OTeF₅)₆^? + NOCl = SbCl₅ + NO⁺ Sb(OTeF₅)₆^?, or oxidatively, using a mixture of Xe(OTeF₅)₂ and Sb(OTeF₅)₅, e.g. C₆F₆ + $\text{1}\text{2}$ Xe(OTeF₅)₂ + Sb(OTeF₅)₅ = C₆F₆⁺ Sb(OTeF₅)₆^? + $\text{1}\text{2}$ Xe.     

Vibrational spectra and internal rotation barriers of cyclopentadienyl germanium trihalides: (C5H5)GeCl3, (C5H5)GeBr3 and (C5H5)GeI3

IR and Raman spectra of gaseous and solid CpGeX₃ species (Cp  C₅H₅ and X = Cl, Br, I) are reported. The results are compared with those obtained previously for CpTiCl₃. Internal rotation barriers and thermodynamic functions are reported.     

Crytal and molecular structure of hydrido(trichlorostannyl)bis-cyclopentadienyl molybdenum(η5-C5H5)2Mo(H)SnCl3

On the basis of X-ray analysis the crystal and molecular structures of (η₅-C₅H₅)₂Mo(H)SnCl₃ have been determined. The compound crystallizes in the monoclinic system with parameters: a = 8.313(3), b = 13.109(4), c = 6.384(2) Å, β = 106.52(2)°, space group P2₁/m, R = 0.028. The conformation occurring in Cp₂Mo(H)SnCl₃ is that with the maximum repulsion between the chloride atoms and the cyclopentadienyl rings. The hydride H atom is shielded by the cyclopentadienyl groups and chlorine atoms, which accounts for the compound's stability to oxygen and hydrolysis.