Separation of microamounts of yttrium from strontium by using sodium dicarbollylcobaltate, Slovafol 909 and ethylenediamine - N, N, N', N'-tetraacetic acid in the water - nitrobenzene extraction system

Summary A rapid extraction separation of trace amounts of yttrium from strontium by a nitrobenzene solution of sodium dicarbollylcobaltate (NaDCC) in the presence of p-nonylphenylnonaethylene glycol (Slovafol 909) and tetrasodium salt of ethylenediamine - N,N,N',N' - tetraacetic acid (Na₄L) in the aqueous phase was developed. The separation factor a(Sr/Y) was substantially higher than 10⁵. This water-nitrobenzene extraction system can be applied for the efficient separation of carrier-free ⁹⁰Y from ⁹⁰Y/⁹⁰Sr generator.     

Extraction of Dy(III) with N,N,N',N'-tetrabutylmalonamide

The extraction behavior of N,N,N',N'-tetrabutylmalonamide (TBMA) employing toluene as diluent toward Dy(III) has been investigated. The effect of the concentrations of nitric acid, lithium nitrate and extractant and also of the temperature on the distribution ratio has been studied. The stoichiometry found for the Dy(III) extracted species suggests a structure such as Dy(NO₃)₃ ^.3TBMA. An attempt has been made to establish the structure of the isolated extracted species recurring to the data of IR.     

Molecular structure and bonding properties of tris(N-methyl-formamide) formamide)(N,N, N', N'-tetramethylethylenediamine)-copper(II) perchlorate

Summary The x-ray crystal structure of tris(N-methylformamide) (N, N, N', N'-tetramethylethylenediamine)copper(II) perchlorate has been determined using three-dimensional x-ray diffraction data. The complex crystallizes in space group P2₁/c with Z=4. The cell dimensions are=8.255(3),b=17.951(6),c=16.541(4) Å, and =91.03(2)°. Least-squares refinement of the structure has yielded a final R value of 4.52% for 2108 independent reflect ions. The square pyramidal structure consists ofN, N, N', N'-tetramethylethylenediamine and twoN-methylformamide ligands forming a basal square plane with Cu–N bond lengths of 2.029(5) and 2.033(5) and Cu–O 1.981(4) and 1.985(4) Å, and a thirdN-methylformamide on the apex with a Cu–O distance of 2.181(4)Å. Each of the molecular plances of the three N-methylformamides lies nearly coplanar with thexy, yz andxz molecular coordination planes. The bonding properties of the title compound and its i.r. and uv-vis spectra are discussed with reference to the structure.     

Oxidation of substituted toluenes with molecular oxygen in the presence of N,N',N' '-trihydroxyisocyanuric acid as a key catalyst

N,N',N' '-Trihydroxyisocianuric acid (THICA) was found to be a very efficient catalyst for the oxidation of alkylbenzenes with dioxygen. Thus, a variety of meta- and para-substituted toluenes bearing an electron-withdrawing substituent such as cyanotoluene, chlorotoluene, and toluic acid under O(2) (1 atm) in the presence of THICA (5 mol %) and Co(OAc)(2) (0.5 mol %) at 100 degrees C were smoothly oxidized to the corresponding benzoic acids in almost quantitative yields. The aerobic oxidation of toluene by THICA was compared with that by N-hydroxyphthalimide. p-Xylene was efficiently oxidized by THICA to telephthalic acid in high yield (over 95%) under mild conditions.     

N,N,N',N'-Tetrabutyladipicamide as a new extractant in toluene of nitric acid and uranium (VI)

N,N,N',N'-Tetrabutyladipicamide (TBAA) was used for the extraction of nitric acid and uranyl(II) ion from nitric acid media into toluene. The effects of nitric acid, uranyl(II) ion, and extractant concentration, temperature and back extraction on the distribution coefficient of uranyl(II) ion have been studied. The main adduct of TBAA and HNO₃ is TBAA·HNO₃ in 1.0 mol/l nitric acid solution. The 1:2:2 complex of uranyl(II) ion, nitrate ion and TBAA as extracted species is further confirmed by IR spectra of the extraction of uranyl(II) ion with TBAA. The values of the thermodynamic parameters have also been calculated.     

Kinetic study on the transfer mechanism of uranyl(VI) ions using N,N,N',N'-tetrabutyladipicamide from nitric acid media

By using stirred-cell method as experimental technique, the kinetictransfer mechanism of UO₂ ²⁺+ with N,N,N',N'-tetrabutyladipicamide(TBAA) from nitric acid solutions into toluene was studied. The differentconditions effecting the extraction rate constants (k'_f and k'_b ) were investigated, such as UO₂ ²⁺ concentration,HNO₃ concentration, TBAA concentration, temperature and agitationspeed. It was found that the extraction process was controlled by the diffusionof UO₂ (NO₃ )₂ . 2TBAA from the liquid-liquidsurface into the organic phase in the range of the experimental concentrationof HNO₃. The extraction rate was found to be of pseudo-first orderwith respect to the concentration of uranium(VI).     

Metal chelates of phosphonate-containing ligands-I Stability of some N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid metal chelates

A potentiometric investigation of the acid dissociation constants of the octabasic ENTMP [N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid] is reported. The stability constants of protonated MH(n)L (n = 1, 2, 3 and 4) and unprotonated ML metal chelates of Mg, Ca, Ba and Cd with ENTMP have been measured. The stabilities are in the order Mg < Ca < Ba < Cd.     

Radiolysis of cobalt(III)-1,2 bis(beta-aminoethoxy)ethane N,N,N',N' sodium sulfonate triacetic acid chelate

Chelation studies of cobalt(III) with 1,2 bis(beta-aminoethoxy)ethane N,N,N',N' sodium sulfonate triacetic acid (ASTA) were performed. The results showed the effectiveness of ASTA as a chelating agent by using: molar ratio, continuous variation and slope ratio methods. Stable complex 1∶1 was formed at pH from 6.0 to 10.5. Solutions of Co-ASTA chelate of different molar ratios at pH 6.5 and 8.0 were irradiated by different gamma-radiation doses. The results showed a linear decrease of absorbance with gamma-radiation dose which can be utilized as a dosimeter for low dose rate measurement in the range studied. A proposed radiolytic mechanism is discussed. The degradation of the ASTA ligand has been related to hydroxyl radical attack.     

Liquid chromatography of lanthanide chelates of 1-(p-nitrophenyl)ethylenediamine-N,N,N',N' -tetra-acetic acid

Preparation of the chelating agent, 1-(p-nitrophenyl)ethylenediamine-N,N,N',N'-tetra-acetic acid (p-nitrophenylEDTA), is described in detail. Separation of p-nitrophenylEDTA chelates of ytterbium(III), erbium(III), dysprosium(III) and europium(III) has been achieved by reversed-phase ion-pair liquid chromatography. With spectrophotometric detection at 254 nm, linear responses over about four orders of magnitude were achieved with detection limits (S/N = 2) of about 0.5 pmole.     

Isotachophoretic determination of stability constants of Ho and Y complexes with diethylenetriaminepentaacetic acid and 1,4,7,10-tetraazadodecane-N,N',N'',N'''-tetraacetic acid

The method of capillary isotachophoresis with conductivity detection was applied for the determination of the physico-chemical characteristics (conditional stability constants log beta') of holmium and yttrium complexes with DTPA (diethylenetriaminepentaacetic acid) and DOTA (1,4,7,10-tetraazadodecane-N,N',N',N'-tetraacetic acid). The log beta' determination is based on the linear relation between the stability constants of lanthanide-DTPA (lanthanide-DOTA) complexes and the reduction of the zone of the complex owing to the bleeding phenomena (liberating free metal ion). The stability constants calculated using this relationship are comparable with the literary data obtained by other methods for both holmium (log beta'(Ho-DTPA)=21.9, log beta'(Ho-DOTA)=24.5) and yttrium complexes (log beta'(Y-DTPA)=21.2, log beta'(Y-DOTA)=24.4). Capillary isotachophoresis was applied for the determination of the optimum composition of the reaction mixture (metal:ligand ratio) as well.     

Kinetics and mechanism of the reaction oftrans-cyclohexane-1,2-diamine-N N N' N'-tetra-acetatomanganate(III) with substituted thioureas in aqueous medium

Summary The kinetics of reduction of [Mn^III(cydta)]^– (where H₄cydta=trans-cyclohexane-1,2-diamine-N N N' N'-tetraacetic acid) by some thiourea reductants have been studied in aqueous solution by stopped-flow techniques in the pH ranges 2.5–4.5 and 9.2–10.2. An initial increase in absorbance followed by a steady decrease indicated the formation of a precursor complex prior to the electron transfer step. The reactions are first order in both oxidant and reductant. The observed increase in rate in going from low to high pH is attributed to the difference in reactivities of the aqua and hydroxo species of the Mn^III complex; the higher reactivity of the latter is consistent with the formation of a ligand-bridged activated species prior to electron transfer. The reactivity order for the thiourea derivatives follows the order of their reported substituent effects.     

Highly cross-linked polymers containing N,N',N' '-chelate ligands for the Cu(II)-mediated hydrolysis of phosphoesters

Three immobilized Cu(II) complexes were generated by the following: (a) homopolymerization of the N,N',N' '-chelate ligand tris[2-(1-vinylimidazolyl)]phosphine (1) and subsequent metalation with CuCl2; (b) copolymerization of 1 with ethyleneglycol dimethacrylate (EGDMA) und subsequent metalation with CuCl2; or (c) molecular imprinting with the organometallic Mo-complex [Mo(eta3-C4H7)(CO)2(1)](TsO) (5) and EGDMA and subsequent replacement of Mo(II) by Cu(II). All three polymeric Cu complexes were found to efficiently promote the hydrolysis of activated phosphoesters with the relative activity being dependent on the nature of the polymer and the substrate.     

Potentiometric behavior of N,N,N',N'-tetrabenzylmethylenediamine-based hydrogen ion-selective electrodes

H(+)-ion selective electrodes (H(+)-ISE) based on N,N,N',N'-tetrabenzylalkylenediamine (alkylene: methylene, ethylene, propylene, hexylene) are prepared. We are compared with their response potentials to carbon numbers between diamino groups. They were showed linear selective to hydrogen ion in the range of pH 1.5-9.0, 2.5-9.0, 3.5-9.0 and 4.0-9.0, and their Nernstian slopes were 57.3, 53.5, 57.4 and 56.1 mV pH(-1) at 20+/-0.2 degrees C (theoretical value: 58.2 mV pH(-1)), respectively. The interference effect on the cations were measured to alkali metal ions, alkaline earth metals ions. Selectivity coefficients were measured by the mixed-solution method. Among all electrodes the N,N,N',N'-tetrabenzylmethylenediamine (TBMDA)-based electrode has shown the best selectivity in acidic solution.     

The formation of 2-hydroxy-1,3-diaminopropane-N,N,N',N'-tetra-acetic acid silver and mercury(III) chelates

The stability constants of mononuclear (1:1) and binuclear (2:1) chelates of the Ag-HDPTA and Hg(II)-HDPTA systems (HDPTA = 2-hydroxy-1,3-diaminopropane-N,N,N',N'-tetra-acetic acid) were evaluated from pM and pH data, using a method proposed earlier by Ringbom and the author. The determinations yielded the following stability constants (concentration): The use of the reagent for the analytical determination of silver and mercury(II) ions is also discussed.     

Synthesis of mono-6-deoxy-6-N,N,N',N',N'-pentamethylethylenediammonio-cyclomaltoheptaose, a single-isomer, monosubstituted, permanently dicationic beta-CD and its use for enantiomer separations by CE

The dichloride salt of mono-6-deoxy-6-N,N,N',N',N'-pentamethylethylenediammonio-cyclomaltoheptaose (PEMEDA-BCD), the first single-isomer, monosubstituted, permanently dicationic beta-CD has been synthesized, analytically characterized, and used for the capillary electrophoretic separation of the enantiomers of a group of analytes in acidic and basic BGEs. When the concentration of PEMEDA-BCD was changed in the BGEs, the resulting effective mobilities of the analytes and the respective separation selectivities followed the predictions of the ionic strength-corrected charged resolving agent migration model. Good separation selectivities and favorable normalized EOF mobilities allowed for the rapid, efficient separation of the enantiomers of anionic, weak acid and nonionic analytes in the low- and/or high-pH BGEs.     

Crystal Structure of Tetrafluoro(1,10-phenanthroline-N,N')silicon Acetonitrile Semisolvate

The crystal structure of tetrafluoro(1,10-phenanthroline-N,N')silicon acetonitrile semisolvate, [SiF₄(phen)]·1/2CH₃CN (I), was studied by X-ray diffraction analysis. The structure of I is tetragonal (space group I4₁/a; a=9.184(1), c=29.700(5) , Z=8); direct methods, full-matrix least-squares refinement in an anisotropic approximation; R=0.039 for all 1820 independent reflections collected (CAD-4 automatic diffractometer, MoK). The geometrical parameters of the [SiF₄(phen)] molecule (bond lengths and angles, etc.) were determined with a high accuracy.     

OLEFIN SYNTHESIS USING LITHIUM DERIVATIVES OF N,N,N',N'-TETRAMETHYLDIAMIDES OF ARYLMETHANEPHOSPHONIC ACIDS

Abstract

The reaction of lithium derivatives of N,N,N',N'-tetramethyldiamides of arylmethanephosphonic acids (1-Li) with aldehydes 2 is studied. It is found that under certain reaction conditions (THF, 5 hrs at -70°C and then allowing to warm to room temperature) the aldol stage of the reaction is highly stereoselective, only erythro adducts (2-hydroxyphosphonamides) 3, 4 being formed in 47–75% yields. By heating of 3 and 4 in neutral medium the corresponding (Z)-olefins 5, 6 are obtained (yields 64–74%). It is established that an acid catalyzed olefination of 2-hydroxyphosphonamides is also possible, but the reaction is not stereospecific.     

Quantitation of N,N,N',N'-tetrakis (2-hydroxypropyl)-ethylenediamine in plasma by gas chromatography

A wide-bore capillary gas chromatographic method with nitrogen-selective thermionic detection is described for the quantitative analysis of N,N,N',N'-tetrakis (2-hydroxypropyl)ethylenediamine (Quadrol) in plasma. N,N,N',N'-tetrakis (2-hydroxybutyl)ethylenediamine is used as an internal standard. Rat or human plasma samples (0.5 ml) are mixed with internal standard, adjusted to alkaline pH and subjected to a single extraction with dichloromethane. Quadrol recovery from plasma typically exceeds 90%. The method is linear over the range 1.0-50 micrograms/ml. The working detection limit is 0.5 microgram/ml and the analysis time is under 7 min. The procedure has been used to obtain plasma concentration versus time data for the evaluation of Quadrol pharmacokinetics in rats.     

Metal complexes of 1-oxa-4,7,10-triazacyclododecane-N,N',N''-triacetic acid

The macrocyclic complexone 1-oxa-4,7,10-triazacyclododecane-N,N',N'-triacetic acid (cODTA) has been synthesized and its protona constants, stability constants of metal complexes and enthalpy changes for the formation of alkaline-earth complexes have been determined. Although it is not so powerful a complexing agent as the N-acetate derivative of the corresponding tetra-aza macrocycle, cDOTA, this is still one of the strongest complexones known, particularly towards the alkaline-earth metals. The complexes of the transition metals are also very stable and there is an inversion of the Irving-Williams order of stability for the complexes of cobalt and nickel.     

Metal chelates of phosphonate-containing ligands-IV (Stability of some 1,6-hexamethylenediamine-N,N,N',N'-tetra(methylenephosphonic) acid metal chelates)

The stability constants of the complexes formed between the anion of 1,6-hexamethylenediamine-N,N,N',N'-tetra(methylenephosphonic) acid and some transition and non-transition metal ions have been measured potentiometrically at a temperature of 25 degrees and an ionic strength of 0.1M (KNO(3)). The acid dissociation constants of the ligand and stability constants of the protonated complexes are also reported. Comparisons are made with the acid dissociation constants of the analogous compounds EDTA, ENTMP and HDTA, and possible structural formulae are given.