过渡金属乙酰丙酮螯合物的体积排除色谱研究

用体积排除色谱方法研究了过渡金属Fe(Ⅲ)、Co(Ⅲ)、Cu(Ⅱ)、Ni(Ⅱ)的乙酰丙酮螯合物在四氢呋喃溶液中的加合和缔合行为。在溶液中乙酰丙酮钴(Ⅲ)以单个螯合物分子的形式存在,乙酰丙酮铜(Ⅱ)和乙酰丙酮铁(Ⅲ)与溶剂加合生成加合物,乙酰丙酮铁(Ⅲ)除加合物外还存在缔合度为2-10的多分散缔合物,乙酰丙酮镍(Ⅱ)水合物在四氢呋喃中产生了加合交换作用,同时存在缔合度为6左右的缔合物。色谱数据给出了螯合物、加合物及缔合物的相对含量。螯合物与相同分子量的聚苯乙烯相比,其保留体积的滞后以Ni相似文献   

Mangan(IV)-Komplexe mit dreizähnigen diaciden Liganden. Kristallstruktur von Acetylacetonato-salicylaldehydbenzoylhydrazonato(2−)-methanol-mangan(III)

Manganese(IV) Complexes with Tridentate Diacidic Ligands. Crystal Structure of Acetyl-acetonato-salicylaldehydebenzoylhydrazonato(2?)-methanol-manganese(III) The manganese(IV) chelates of salicylaldehyde benzoylhydrazone and salicylaldehyde salicylhydrazone were synthesized by ligand exchange reactions using bis(acetylacetonato)manganese(II), tris(acetylacetonato)manganese(III) as well as manganese(III) acetate. The brown complexes show the expected molecular ions in the APCI mass spectra. As an intermediate compound acetyacetonato-salicylaldehydebenzoylhydrazonato(2?)-methanol-manganese(III) was isolated and characterized by X-ray structural analysis. Crystallographic data see “Inhaltsübersicht”.     

SOLVATION OF ALUMINIUM(III) AND IRON(III) COMPLEXES OF HYDROXAMATE LIGANDS IN ALCOHOL-WATER MIXTURES

Abstract

Solubilities and derived transfer chemical potential trends are reported for several tris(hydroxamato)-aluminium(III) and iron(III) complexes in methanol-water and in t-butylalcohol-water solvent mixtures. These trends are discussed in terms of hydrophilic and hydrophobic characteristics of the peripheries of these complexes.     

COMPLEXES OF GALLIUM(III) WITH HYDROXYAROMATIC LIGANDS

Abstract

The equilibria between gallium(III) ion and selected hydroxyaromatic and dihydroxyaromatic ligands at 25°C, μ=0.100 M (KNO₃) have been determined. Potentiometric measurements on 1:1, 2:1, and 3:1 molar ratios of ligand to Ga(III) have been made as a function of degree of neutralization over the entire accessible ?log [H⁺] scale. Calculations were carried out so as to take account of competing hydrolytic reactions, and formation constants of gallium(III) with chromotropic acid, 8-hydroxyquinoline-5-sulfonic acid, 5-sulfosalicylic acid, and 1,2-dihydroxy-benzene-3,5-disulfonic acid were obtained. Stable hydroxo chelates do not form under the reaction conditions employed. The protonation constants of the ligands and the formation constants of the gallium chelates are discussed and compared with previously published work on these gallium chelates and on chelates of “analogous” metal ions such as those of Fe(III) and A1(III).     

Complexation and the laser luminescence studies of Eu(III), Am(III), and Cm(III) with EDTA,CDTA, and PDTA and their ternary complexation with dicarboxylates

Spectroscopy has been used to determine the number of coordinated water molecules bound to Eu(III) and Cm(III) in a series of binary complexes of polyaminocarboxylate and their ternary complexes with dicarboxylates as well as with similar ligands with additional O-, N-, and S-donors. Complexes of Eu(III) and Cm(III) with polyaminocarboxylate alone contain ca. 2.5–3.0 waters of hydration. Increasing the steric requirement of a polyaminocarboxylate by increasing the number of groups in the ligand backbone does not appreciably change the hydration of these cations. The stability constants of the binary and ternary complexes of Cm(III), Am(III), and Eu(III) with these ligands were measured by solvent extraction in a solution of 0.1 M (NaClO₄). The size, basicity, specific M³⁺-second ligand interactions, and steric requirement of the ligands are the factors which affect the ternary complexation. Knowledge of the chemical species formed by actinide cations with organic ligands (carboxylates and aminocarboxylates), which are present in all nuclear waste, is important to understand the behavior of waste forms and the migration behavior of actinides in the environment.     

Iron(III) and nickel(II) template complexes derived from benzophenone thiosemicarbazones

New iron(III) and nickel(II) chelates were synthesized by template reaction of 2,4-dihydroxy- and 2-hydroxy-4-methoxy-benzophenone S-methylthiosemicarbazones with 2-hydroxy- and 5-bromo-2-hydroxy-benzaldehydes. The template complexes were isolated as stable solids and characterized by elemental analysis, conductivity and magnetic measurements, IR, ¹H NMR, UV–Visible, and mass spectra. The crystal structure of N ¹-(2-hydroxy-4-methoxyphenyl)(phenyl)methylene-N ⁴-(2-hydroxy-phenyl)methylene-S-methyl-thiosemicarbazidato-Fe(III) was determined by X-ray diffraction. A five-coordinate, distorted square-pyramidal geometry was established crystallographically for the iron(III) complex. Cytotoxicity and proliferation properties were determined using human erythromyeloblastoid leukemia and HL-60 mouse promyelocytic leukemia cell lines. For K 562 and HL-60 cells, compounds 1a and 2b were found to be cytotoxic at concentrations of 10 and 20 µg mL^?1.     

Thin Layer Chromatography of Metal Ions Complexed with Anils (VII) Detection,Separation, and Determination

Abstract

Dark colored chelates of p-dimethylaminoanil of 3-benzoyl-methylglyoxal bidentate ligand with Sb(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), ZrO(II), Y(III), La(III), Pr(III), Nd(III) Sm(III), Gd(III) and Dy(III) have been chromatographed on starch bound silica gel thin layers. New correlations of I.R. with R_f (resolving solvent) have been used to ascertain the colored spots.

Among various mixtures resolved qualitatively a few typical ones have been alanysed quantitatively. Errors in determinations and maximum separation limits have also been deduced.     

Spectrophotometry Determination of Arsenic(III) and Antimony(III) by Means of Isonicotinoylhydrazones of 4-Dimethylaminobezaldehyde (4-Dbih) and 2-Hydroxynaphthaldehyde (2-Hnih)

Abstract

4-DBIH and 2-HNIH react with As(III) and Sb(III) respectively, in CH₃COOH medium to form colored complexes stable in presence of EDTA. As(III) and Sb(III) do not react with 2-HNIH and 4-DBIH respectively, and the Sb(III)-2-HNIH complex is extractable into isoamyl alcohol. These behaviours were used for the spectrophotometry determination of As (III) and Sb(III) in presence of several cations.     

The Affinity of Gallium(III) and Indium(III) for Nitrogen Donor Ligands

Abstract

Dedicated to Professor Arthur Martell on the occasion of his seventy fifth birthday.

The complexes of In(III) and Ga(III) with a variety of nitrogen donor ligands were studied in aqueous solution by glass electrode potentiometry at 25°C in 0.1 M NaNO₃. The ligands were 2-aminomethylpyri-dine (AMPY), ethylenediamine (EN), N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (THPED), and N,N-bis(2-hydroxyethyl)glycine (BICIN). A variety of mixed ligand complexes of the MLOH type were detected with many of the above ligands as L. The logK₁ values obtained were with Ga(III) 8.40 (AMPY), 7.94 (THPED) 12.72 (EN), and In(III) 7.6 (AMPY), 8.20 (THPED), and 7.06 (BICIN). These formation constants are discussed in relation to previous predictions that In(III) and Ga(III) would have a substantial chemistry with nitrogen donor ligands. Of particular interest is the Ga(III) system with EN, where a very stable Ga(EN)³⁺ complex is formed, but no higher complexes except for hydrolyzed species such as Ga(EN)OH²⁺ and Ga(EN)(OH)₂ ⁺.     

Fluorometric Determination of Iron(Iii) with O-Hydroxyhydroquinonephthalein in the Presence of Brij 58

Abstract

A highly sensitive fluorescence reaction of iron(III) with o-hydroxyhydroquinonephthalein (Qnph) in the presence of various surfactants, and its application to the fluorophotometry of trace amounts of iron(III) is described. the method is based on the fluorescence quenching reaction between Qnph and iron(III) in the presence of Brij 58 at pH 3–4. the quenching calibration graph was linear over the range 0 – 300 ng per ml iron(III) by using fluorescence reaction at Em 525 nm with Ex 470 nm, and the iron(III) detection limit was 5 ng/ml. the proposed method is simple, rapid and does not involve heating or solvent extraction.     

Activation of Iron (III) and Bismuth (III) Nitrates by Tungstophosphoric Acid: Solvent‐Free Oxidative Deprotection of Oximes to Carbonyl Compounds

Abstract

Tungstophosphoric acid (H₃PW₁₂O₄₀ · 6H₂O) has been used as a catalyst for a simple, rapid, selective, and solvent‐free cleavage of oximes to carbonyl compounds using iron (III) and bismuth (III) nitrates as oxidants.     

Advanced Synthesis of Dihydrofurans: Effect of Formic Acid on the Mn(III)-Based Oxidation

The Mn(III)-based oxidation of a tertiary alkylamine, such as nitrilotris(ethane-2,1-diyl) tris(3-oxobutanoate) (1) with 1,1-diphenylethene (2a), effectively proceeded in an acetic acid–formic acid mixed solvent to give nitrilotris(ethane-2,1-diyl) tris(2-methyl-5,5-diphenyl-4,5-dihydrofuran-3-carboxylate) (3). Other typical Mn(III)-based reactions of various β-diketo esters 4a–e, 2,4-pentanedione (6a), malonic acid (6b), and diethyl malonate (6c) with 1,1-diarylthenes 2a–d were also investigated in a similar acetic acid–formic acid mixed solvent and the reaction rate was accelerated and the product yield increased.     

SYNTHESIS AND CHARACTERIZATION OF THE FORMAL Ni(III) AND Cu(III) COORDINATION COMPLEXES OF THE NEW 1,2-DITHIOLENE, 1,4-BUTANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE

Abstract

The new 1,2-dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate, has been isolated. In addition, new monoanionic bis-complexes with nickel and copper have been prepared and isolated. The formal Ni(III) complex crystallizes in the orthorombic space group, P_bca, with a = 9.762(9), b = 12.53(2), and c = 23.166(3) Å, with 4 molecules in the unit cell. The structure was refined to an R = 9.01% (R_w = 8.95%). The formal Cu(III) complex crystallizes in the monoclinic space group, C_2/c, with a = 25.567(6), b = 8.011(3), c = 14.504(3) Å, and β = 106.17(2)° with 4 molecules in the unit cell. The structure refined to R = 4.2% with R _w = 4.3%. Comparisons to similar 1,2-dithiolenes suggest this ligand produces only modest structural and electronic differences when compared to the 1,3-propanediyldithioethylene-1,2-dithiolate complexes. The oxidation (to a neutral complex) and reduction (to a dianion) for the Ni(III) and Cu(III) complexes show large differences from those of maleonitriledithiolate. Other physical data are presented as well.     

Spectroscopic properties and Judd-Ofelt theory analysis of erbium chelates

Erbium chelates including tris(acetylacetonato) erbium(III) monohydrate, tris(acetylacetonato)(1,10-phenanthroline) erbium(III) and tris(trifluoroacetylacetonato)(1,10-phenanthroline) erbium(III) are synthesized. Judd-Ofelt theory is employed on basis of the UV-Vis-NIR absorption spectra of erbium chelates dissolved in methanol. Judd-Ofelt parameters of erbium chelates are determined by a least square fitting and dealt with the chemical structure of erbium chelates. Photoluminescence characteristics of erbium chelates are investigated upon excitation at 488 nm by an Ar(+) laser. The qualitative correlation of Judd-Ofelt parameters with photoluminescence properties for erbium chelates is also discussed. It is found that larger Omega(6) value for erbium chelate is and larger photoluminescence intensity at 1.54 microm is, and Omega(2) value should contribute to the photoluminescence full width at half maximum (FWHM) at 1.54 microm. The changes of Judd-Ofelt parameters result from the introduction of the second ligand phenathroline or the substitution of electron-drawing group CF(3) in beta-diketone for erbium chelates.     

Synthesis,crystal structure and antibacterial activity of manganese(III) and cobalt(III) complexes containing pentadentate Schiff bases of a common amine and thiocyanate

Abstract

Four new mononuclear Schiff base manganese(III) and cobalt(III) complexes viz. [Mn(L¹)(NCS)] (1), [Mn(L²)(NCS)] (2), [Co(L³)(NCS)] (3), and [Co(L⁴)(NCS)]·0.5CH₃OH·0.5H₂O (4), containing thiocyanate as a common pseudohalide ion are reported. The pentadentate Schiff base ligands H₂L¹, H₂L², H₂L³, and H₂L⁴ were obtained by the condensation of substituted salicylaldehydes with N-(3-aminopropyl)-N-methylpropane-1,3-diamine. The syntheses of the complexes have been achieved by the reaction of manganese(II) perchlorate or cobalt(II) perchlorate with the respective Schiff bases in the presence of thiocyanate in methanol medium. Complexes 1–4 have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 1–4 adopt nearly similar structures containing the MN₄O₂ (M?=?Mn, Co) chromophore in which each central M(III) ion adopts a distorted octahedral geometry. Weak intermolecular H-bonding interactions are operative in these complexes to bind the molecular units. The antibacterial activity of 1–4 and their constituent Schiff bases has been tested against some common bacteria.     

1,3-Dimethyl-2-phenyl-1,3-diazaphospholidine-2-oxide as ligand for the preparation of luminescent lanthanide complexes

Abstract

Europium(III) coordination compounds having general formula [Eu(β-dike)₃L₂] (β-dike?=?dibenzoylmethanate, tenoyltrifluoroacetonate; L?=?1,3-dimethyl-2-phenyl-1,3-diazaphospholidine-2-oxide) were isolated and characterized. The complexes exhibited bright red emission associated to the ⁵D₀→⁷F_J transitions of the metal center upon excitation with near-UV light, with intrinsic quantum yields around 51% and 65%, respectively, for the dibenzoylmethanate and tenoyltrifluoroacetonate derivatives. More information about the behavior of 1,3-dimethyl-2-phenyl-1,3-diazaphospholidine-2-oxide as an antenna-ligand towards trivalent lanthanide ions was obtained by its coordination to [Ln(NO₃)₃] (Ln?=?Eu, Gd, Tb) metal fragments.     

Microdetermination of Heavy Metal Chelates by High-Performance Liquid Chromatography

Abstract

Adsorption chromatography of diethyldithiocarbamate chelates of heavy metals is described. Determination of heavy metals including Hg (II), Cd (II), Pb (II), Cr (VI), Bi (III) and Cu (II) in micro to nano gram order is successfully carried out with good accuracy and reproducibility by a deactivated silica gel column. Separative microdetermination of these chelates is accomplished within 12 min, and selective determination is also possible by choosing the detection wavelength of a UV detector.     

CRYSTAL STRUCTURE OF THE ISOMORPHOUS COMPLEXES TETRAAQUABIS(2,6-DIHYDROXY-BENZOATO-O)(2,6-DIHYDROXY-BENZOATO-O,O)TERBIUM(III) AND HOLMIUM(III) DIHYDRATE

Abstract

The structures of isomorphic Tb(III) and Ho(III) complexes with 2,6-dihydroxybenzoic acid of formula [Tb(C₇H₅O₄] 2H₂O and [Ho(C₇H₅O₄)₃ 4H₂O] 2H₂O has been determined by X-ray diffraction and refined to a residual R = 0.030 for 5376 observed reflections and R = 0.0284 for 5660 observed reflections, for Tb(III) and Ho(III) complexes, respectively. Crystals are triclinic, space group P1 with a= 10.748(2), b=11.309(2), c = 12.452(2)Å, α = 82.28(3), ? = 73.05(5), γ = 68.27(3)° for Tb(III) and a= 10.731(2), b=11.269(2), c = 12.436(2)Å, α = 82.25(3), β = 72.92(3), γ = 68.46(3)° for Ho(III).

In the structure of these monomelic complexes the metal ions are coordinated by oxygen atoms of one bidentate chelating and two monodentate carboxylate groups and four molecules of water. Tb-O distances are in the range 2.323(3)-2.506(3) Å and Ho-0 2.297(3)-2.486(3) Å. The crystal structure, consisting of discrete units of neutral complexes with two molecules of water of crystallization is stabilized by intra-and intermolecular hydrogen bonds.     

Synthesis,spectral and antimicrobial studies of chloroantimony(III)di[3(2′-hydroxyphenyl)-5-(4-substitutedphenyl)pyrazolinates]

Dichloroantimony(III) pyrazolinates and chloroantimony(III) dipyrazolinates of the type SbCl₂(C₁₅H₁₂N₂OX) and SbCl(C₁₅H₁₂N₂OX)₂ [where C₁₅H₁₂N₂OX = 3(2′-hydroxyphenyl)-5-(4-X-phenyl)pyrazoline, X=H in1 and5;–CH₃ in2 and6;–OCH₃ in3 and7 and–Cl in4 and8] have been synthesized by reaction of SbCl₃ and sodium salt of pyrazolines in 1 : 1 and 1 : 2 molar ratio in anhydrous benzene at elevated temperature. These newly synthesized derivatives have been characterized by elemental analysis (C, H, N, Cl and Sb), molecular weight measurement and spectral studies [IR and¹H and¹³C NMR]. The free pyrazoline and some dichloroantimony(III) pyrazolinates and chloroantimony(III) dipyrazolinates have been screened for antibacterial and antifungal activities, with some dichloroantimony(III) pyrazolinates and chloroantimony(III) dipyrazolinates exhibiting higher antibacterial and antifungal effects than free pyrazoline and some antibiotics.     

Untersuchung Der Kcmplexbildung Von Thallium(III) Mit 1-Phenyl-3-Methyl-4-Benzoylpyrazolon-5

Abstract

A study has been made of the method used for extracting the complex formed between thallium(III) and PhMBP. It has been demonstrated that thallium(III) can be readily extracted as a complex with PhMBP by organic solvents at low pH. The extraction of thallium(III) has been studied as a function of pH, concentration of reagent, nature of solvent, duration of contact of the phases and concentration of thallium(III). It has been established that thallium(III) forms a complex with PhMBP of the type MA_n, where n=3. The stability constants and distribution constant of the neutral complex has been calculated by the method of Leden-Rydberg.