Radiation-chemical changes of benzo-15-crown-5 in chloroform

NMR, IR and MS were used for identification of major products of radiolysis of benzo-15-crown-5 in chloroform. The crown ether exhibits high affinity towards inorganic products of radiolysis of chloroform resulting in the formation of complexes.     

苯并-15-冠-5和二苯并-18-冠-6萃取分离铟(III)的研究

本文用斜率法、饱和法以及通过与萃取合物相对应的冠醚配合物晶体的制备及其性质研究, 探讨了In^3^+的萃取机理, 测定并计算了表观萃取平衡常数, 将此萃取体系应用于铟和某些体系应用于铟和某些金属离子的萃取分离, 亦获得较好的结果.     

Complexation of tetrafluoroboric acid with benzo-15-crown-5

Russian Chemical Bulletin - The extraction of tetrafluoroboric acid from aqueous solutions to a solution of benzo-15-crown-5 (B15С5, 1 mol L-1) in chloroform is shown to occur due to...     

苯并-15-冠-5四溴合铟酸钾配合物的晶体结构

苯并-15-冠-5-四溴合铟(III)酸钾,KInBr~4(C~14H~20O~5)~2,晶体属单斜晶系,空间群为C~2h^5-P2~1/n,晶胞参数a=14.402(3),b=15.082(3),c=17.262(5)A,β=93.42(2),Z=4.非氢原子的位置由Patterson函数及Fourier合成法找出,经全矩阵最小二乘法修正R=0.057.结构分析表明K^+和两个苯并-15-冠-5(B-15-C-5)分子直接配位,对阴离子为InBr~4^-,具有四面体构型.InBr~4^-与配阳离子K(B-15-C-5)~2^+依靠静电引力结合为离子对.由此说明,In(III)在过量KBr存在下可以被B-15-C-5定量地萃取至有机相中.     

Impregnated type sorbents based on benzo-15-crown-5 for gold(III) extraction from hydrochloric solutions

Russian Chemical Bulletin - A series of sorbents based on benzo-15-crown-5, various supports (styrene-divinylbenzene LPS-500, hydrophobized silica gel), and diluents (octan-1-ol, nitrobenzene,...     

Extraction of Nd(III), Tb(III) and Lu(III) with picrolonic acid in methylisobutylketone

The extraction of Nd(III), Tb(III) and Lu(III) as representatives of lanthanide(III) ions with picrolonic acid (HPA) in methylisobutylketone (MIBK) has been studied from pH 1-2 buffer solutions. The composition of the organic species formed in the organic phase after extraction has been determined by slope analysis to be M(PA)₃ [M = Nd(III), Tb(III) and Lu(III)]. The equilibrium constant values, log k _ex This revised version was published online in July 2006 with corrections to the Cover Date.     

Polymethine dyes based on (benzo-15-crown-5) thiazole

Several monomethinecyanine, merocyanine and styryl dyes were synthesized using a 5,6-(1,4,7,10,13-pentaoxacyclotridecane)-benzothiazole derivative as the starging reageni. A study was made of their spectral characteristics and the effect which complexing with alkaline and alkaline-earth metal salts had on their chromaticity.Organic Chemistry Institute, National Academy of Sciences of Ukraine, Kiev. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 992–996. Original article submitted March 12, 1996.     

Extraction of Sm(III), Gd(III) and Ho(III) ions with picrolonic acid in methylisobutylketone

Summary Picrolonic acid (HPA) in methylisobutylketone (MIBK) (0.01 mol^. dm^-3) has been used for the extraction of lanthanide(III) ions such as Sm(III), Gd(III) and Ho(III) (Me) (~3^. 10^-6mol^. dm^-3) from pH 1-2 buffer solutions of 0.1 mol^. dm^-3(H⁺, Cl^-) ionic strength and quantitative extraction (>95%) was found at pH 2. Through slope analysis the composition of the organometallic adduct responsible for the extraction came out to be M(PA)₃. The conditional equilibrium constant values, log K_ex, were deduced to be 2.60±0.01, 2.09±0.01 and 1.44±0.03 for these lanthanide(III) ions, respectively. The metals in concentration up to ~2.5^. 10^-4mol^. dm^-3can be quantitatively extracted by the proposed system. Among the various anions, fluoride, oxalate and cyanide ions (~3.0^. 10^-4mol^. dm^-3) and, among the cations, Zn(II) Cu(II), Co(II) and Fe(III) reduced the lanthanide extraction. The extraction of various other metal ions at the optimized conditions of Me extraction for this series of lanthanide ions was also studied and high separation factors (10²-10³) were obtained showing the good selectivity of this extraction system.     

Synergic solvent extraction of some lanthanides with mixtures of thenoyltrifluoroacetone and benzo-15-crown-5

Summary The synergic solvent extraction of Pr, Gd, and Yb with mixtures of thenoyltrifluoroacetone (HTTA) and a crown ether benzo-15-crown-5 (B15C5) in CCl₄, C₆H₆ and CHCl₃ has been studied. The composition of the extracted species has been determined asLn(TTA)₃·2B15C5 (Ln=Pr, Gd, and Yb). The values of the equilibrium constants have been calculated.

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Synergetische Extraktion von Lanthaniden mit Thenoyltrifluoraceton und Benzo-15-crown-5

Zusammenfassung Es wurde die synergetische Extraktion von Pr, Gd und Yb mit Mischungen ausHTTA und Benzo-15-crown-5 in CCl₄, C₆H₆ und CHCl₃ untersucht. Die Zusammensetzung der ExtraktionskomplexverbindungenLn(TTA)₃·2B15C5 (Ln=Pr, Gd und Yb) wurde bestimmt, und die Gleichgewichtskonstanten wurden berechnet.

     

The extraction of thulium(III), dysprosium(III) and samarium(III) by dioctylarsinic acid in chloroform

Dioctylarsinic acid, HDOAA, in chloroform (0.1 M) extracts thulium(III), dysprosium(III) and samarium(III) from their aqueous solutions in the pH ranges 1–6.5, 2–7 and 4–8, respectively, with extraction coefficients of approximately 0.1 for the lowest and 10 for the highest pH. The extractability increased with increasing ionic strength for each ion and decreased in the order ClO₄^- > NO₃^- > Cl^- > SO₄^2- > acetate for solutions of the same molarity. pH-Dependence curves had slopes ranging from 1.05 to 1.87. The reagent-dependence studies gave curves with slopes between 3.60 and 5.30. The general formula [MX_n(DOAA)_m(HDOAA)_p(H₂O)_q] (X = Cl^-. NO₃^-, SO₄^2-/2, ClO₄^-, acetate, OH^-; n+m=3, m+p=4 or 5, q?0)is suggested for the extracted species.     

Synergistic extraction of Eu(III) and Nd(III) from aqueous medium using a mixture of sulfasalazine and 1,10-phenanthroline

Journal of Radioanalytical and Nuclear Chemistry - Solvent extraction of Eu(III) and Nd(III) from aqueous medium was investigated by sulfasalazine in benzoyl alcohol as single extractant and then...     

Thermal decomposition of metal complexes V. Lanthanide(III) complexes of benzo-15-crown-5

Thermal dissociation reactions of lanthanide(III) nitrates and thiocyanates solid complexes of the cyclic polyether benzo-15-crown-5 were studied in dynamic atmosphere of dry nitrogen and under reduced pressure (5·10^?2 mm Hg). The complexes of lanthanide nitrates undergo dissociation with ligand decomposition while from those of lanthanide thiocyanates the ligand is released undecomposed. Values of enthalpy change and “activation energy” for the dissociation reactions of the complexes with lanthanide thiocyanate were obtained and briefly discussed.     

Cation-Induced dimerization of nickel(II), platinum(II), and palladium(II) meso-tetra(benzo-15-crown-5)porphyrinates

Cation-induced dimerization of nickel(II), platinum(II), and palladium(II) meso-tetra(benzo-15-crown-5)porphyrinates (Ni(II)TCP, Pd(II)TCP, and Pt(II)TCP) on treatment with potassium thiocyanate in a chloroform-methanol solution has been studied by electronic absorption spectroscopy. The formation of [{MTCP}₂(K⁺)₄](SCN^?)₄ in solution induces a hypsochromic shift of the Soret band and a bathochromic shift of the β-band with respect to their positions in the spectrum of MTCP. The equilibrium constants (K) for the 2MTCP + 4K⁺ = [{MTCP}₂(K⁺)₄] processes at 20°C are determined to be as follows: log K _Ni(II)TCP = 27.31 ± 1.67, logK _Pd(II)TCP = 27.16 ± 1.43, and logK _Pt(II)TCP = 26.15 ± 1.56.     

Studies on the thermal behaviour and decomposition mechanism of complexes of rare earth(III) nitrates) with benzo-15-crown-5

Thermal dissociation reactions and mechanism of complexes of rare earth(iii) nitrates with the crown ether benzo-15-crown-5 were investigated by means of TG-DTG, DSC, DTA and IR technique. The results have shown that the dissociation processes of the complexes consist of several steps, one of which is a fast decomposition reaction. The fast decomposition peak temperatures (DSC) of all the complexes of the lanthanides (except Pm and Tm) decrease regularly with increasing atomic number. Moreover, values of the enthalpy change of desolvation, fast and the fourth step of decomposition and the apparent activation energies of fast and the fourth step of decomposition were obtained.

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Zusammenfassung Mittels TG-DTG-, DSC-, DTA- und IR-Techniken wurden einschließlich Mechanismus die thermischen Dissoziationsreaktionen von Komplexen der Seltenerden(III)nitrate mit dem Titelkronenether untersucht. Die Ergebnisse zeigen, daß die Dissoziationsvorgänge der Komplexe aus mehreren Schritten bestehen, von denen einer eine schnelle Zerfallsreaktion ist. Die Peaktemperaturen für die schnellen Zersetzungen (DSC) aller Lanthanidenkomplexe (ausgenommen Pm und Tm) sinken mit ansteigender Ordnungszahl der Lanthaniden ständig im Wert. Außerdem wurden Werte für die Enthalpieänderungen bei der Desolvatation, für den schnellen und den vierten Zersetzungsschritt und für die Aktivierungsenergien des schnellen und vierten Zersetzungsschrittes erhalten.

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The authors express their gratitude to Gan-Che Wang, Xi-Mei Guo and Xi-Ning Xu for their assistance.     

Complexes of benzo-15-crown-5 with protonated primary amines and diamines

Three complexes of benzo-15-crown-5 (B15C5) with protonated primary amines [PhCH₂NH₃(B15C5)](ClO₄), [p-C₆H₄(CH₂NH₃)₂(B15C5)₂](ClO₄)₂, and [(CH₂)₄(NH₃)₂(B15C5)₂](SCN)₂ were isolated and studied in acetonitrile solutions by NMR, and in the solid state by X-ray crystallography. In all complexes, one B15C5 molecule was bound with each R-NH₃⁺ moiety with characteristic small separation of 1.84-1.86 Å between the nitrogen of the R-NH₃⁺ group and the O₅ mean plane of the crown residue. No sandwich-type complexes with a 1:2 R-NH₃⁺/B15C5 stoichiometry were observed. Binding affinities of B15C5 in acetonitrile were similar for all ammonium cations studied: K₁=550±10 M⁻¹ for [PhCH₂NH₃]⁺; K₁=1100±100 and K₂=400±30 M⁻¹ for [p-C₆H₄(CH₂NH₃)₂]²⁺; and K₁=1100±100 and K₂=300±30 M⁻¹ for [H₃N(CH₂)₄NH₃]²⁺. The complexation is primarily enthalpy-driven (ΔH°=−4.9±0.5 kcal/mol, ΔS°=−3.8±1.0 eu for PhCH₂NH₃⁺-B15C5), as determined by variable temperature ¹H NMR titrations.     

Synergistic solvent extraction of Eu(III) and Tb(III) with mixtures of various organophosphorus extractants

Synergistic solvent extraction of Eu(III) and Tb(III) from thiocyanate solutions with mixtures of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHPNA) and di-2-ethylhexylphosphoric acid (DEHPA) or tributyl phosphate (TBP) or trioctylphosphine oxide (TOPO) or triphenylphosphine oxide (TPhPO) in benzene has been studied. The mechanism of extraction can be explained by a simple chemically based model presented in this paper. The equilibrium constants of the mixed-ligand species of the various neutral donors have been determined by non-linear regression analysis.