Anna Malinowska

2,4′-Bipyridyl complexes with cobalt(II) and nickel(II)

SummaryComplexes of empirical formulae [ML2Cl2(OH2)2], [CoL2Br2(OH2)2]L·4H2O, [NiL2Br2(OH2)2]L2·2H2O, [ML2(OH2)4]L2(NO3)2 and [ML4(OH2)2](ClO4)2·2H2O (M = CoII, NiII, L = 2,4′-bipyridyl) were synthesized and characterized by elemental and spectral analyses. The thermal decomposition of the complexes was also investigated.

2,4′-Bipyridyl complexes with silver(I) and copper(II)

SummaryAgI and CuII complexes with 2,4′-bipyridyl (2,4′-bipy or L) with the general formulae AgL2X (where X = NOinf3sup−or ClO4-), CuL2X2·2H2O (X = Cl- or Br-), CuL4SO4·4H2O, CuL4(NO3)2·2H2O and CuL4(ClO4)2·H2O have been isolated pure and characterized by analytical, spectral and magnetic measurements. The thermal decomposition of these complexes was studied under non-isothermal conditions in air.

The complexation of cadmium acetate and propionate by phenanthroline. Structure and properties of [Cd(CH3COO)2(C12H8N2)(H2O)] · H2O and [Cd(CH3CH2COO)2(C12H8N2)]2 · 2CH3CH2COOH

The coordination compounds [Cd(CH3COO-κO 1,O 2)2(phenanthroline-kN 1 N 2)(H2O)] · H2O (1) and [Cd{μ-(CH3CH2COO-κO 1,O 2)}2(phenanthroline-κN 1,N 2)]2 · 2CH3CH2COOH (2) were synthesized and characterized by elemental and thermal analysis and IR spectroscopy. Crystal and molecular structures of both compounds were determined. The complexes are air stable and fairly soluble in water. In both compounds the cadmium is seven-coordinate and contains chelating phenanthroline and two chelating carboxylate groups in the inner coordination sphere. The seventh coordinating oxygen belongs to water in 1 and to bridging carboxylate in 2. All carboxylate groups are bonded unsymmetrically to the central atom. The coordination polyhedra can be described as distorted pentagonal bipyramid (compound 1) and distorted capped tetragonal bipyramid (compound 2). In the structure of 1 intermolecular O(water)–H ··· O (water/carboxylate) hydrogen bonds create a two-dimensional net along the crystallographic a0c plane. Each molecule of 2 is connected to two propionic acid molecules via hydrogen bonds. In both compounds exist π-stacking interactions. †Deceased.

Solvent extraction of lanthanide ions with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP), III: Extraction of gadolinium(III), terbium(III), dysprosium(III), holimum(III), and thulium(III) byHPMBP from aqueous solutions

SummaryThe solvent extraction behaviour of Gd(III), Tb(III), Dy(III), Ho(III), and Tm(III) has been investigated using 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP or HL) in carbon tetrachloride as the extractant. Depending on the concentration ofHPMBP in the organic phase the chelatesLnL3 [Ln(III)=Gd, Tb, Dy, Ho, Tm] and adductsLnL3 · HL [Ln(III)=Gd, Tb, Dy, Ho] were extracted. The extraction equilibrium constants (Kex3 orKex4) for the formation ofLnL3 orLnL3 · HL and the two-phase stability constants of the chelates or adducts (β3x, β4x) have been evaluated.ZusammenfassungDie Extraktion von Gd(III), Tb(III), Dy(III), Ho(III), und Tm(III) mittels 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HPMBP oderHL) in Kohlenstofftetrachlorid wurde untersucht. In Abhängigkeit von der Konzentration anHPMBP in der organischen Phase bildeten sich Chelate vom TypLnL3 [Ln(III)=Gd, Tb, Dy, Ho, Tm] and Addukte vom TypLnL3 · HL [Ln(III)=Gd, Tb, Dy, Ho]. Die Werte der Extraktions-Gleichgewichtskonstanten (Kex3 oderKex4) fürLnL3 oderLnL3 · HL, sowie die Zweiphasen-Beständigkeitskonstanten (β3x, β4x) der Chelate oder Addukte wurden berechnet.

Solvent extraction of lanthanide ions with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP), II. Extraction of erbium(III), ytterbium(III) and lutetium(III) by HPMBP from aqueous-methanol solutions

The solvent extraction of lanthanides(III) (Ln=Er, Yb, Lu) by 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HL) in carbon tetrachloride from aqueous-methanol phase was investigated. The equilibrium constants for the extraction from aqueous −50% (v/v) methanol phase (Kex), two-phase stability constants of the complexesLnL3 (β3*) and stability constants of complexesLnL2+,LnL2+,LnL3 (βn) (Ln=Yb, Lu) were calculated. It was confirmed that the addition of methanol to the aqueous phase causes a synergistic effect. The influence of methanol on the dissociation constant of HPMBP (Ka) and the distribution constant of HPMBP (pHL) between carbon tetrachloride and water-methanol solutions was investigated.ZusammenfassungDie Extraktion von Lanthaniden (Ln=Er, Yb, Lu) mittels 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HL) in Kohlenstofftetrachlorid aus Wasser-Methanol Phase wurde untersucht. Die Werte der Gleichgewichtskonstante für Extraktion aus Wasser −50% (v/v) Methanol-Phase (Kex), der zweiphasigen Beständigkeitskonstante für die KomplexeLnL3 (β3*), sowie der Stabilitätskonstante des KomplexesLnL2+,LnL2+ undLnL3 (βn) (Ln=Yb, Lu), wurden berechnet. Es wurde festgestellt, daß die Zugabe von Methanol zur wäßrigen Phase einen synergistischen Effekt hat. Der Einfluß von Methanol auf die Dissoziationskonstante von HPMBP (Ka) und die Verteilungskonstante des HPMBP (pHL zwischen organischer und wäßrig-methanolischer Phase wurde untersucht.

Complex formation studies on Ho(III) and Lu(III) with 1-(2-pyridylazo)-2-naphthol (PAN) in alcohol-water solutions

The formation ofPAN complexes in the systemsLn(III)—PAN—alcohol-water (where:Ln(III)=Ho, Lu and alcohol=ethanol,n-propanol,iso-propanol) was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn3+ + HL⇌LnL2+ + H+ (HL=PAN) and stability constants of complexesLnL2+ were calculated.

Solvent extraction of rare earth metal ions with 1-(2-pyridylazo)-2-naphthol (PAN)@@@Extraktion von Ionen der Seltenerdmetalle mit 1-(2-Pyridylazo)-2-naphthol (PAN), 5. Mitt.: Komplexbildung und Gleichgewichtsverteilung von Thulium (III) mitPAN: V. Complex formation and distribution equilibria of thulium(III) withPAN

The formation of the Tm(III) complex with 1-(2-pyridylazo)-2-naphthol (PAN or HL) in aqueous-methanol mixtures (50 and 75%v/v) was studied by a spectrophotometric method. The equilibrium constant for the complexing reaction and the stability constant of the complex TmL2+ were calculated. The solvent extraction of Tm(III) byPAN in carbon tetrachloride from aqueous and aqueous-methanol phase was investigated. The extraction equilibrium constants and two-phase stability constants for the TmL3 and the TmL3(MeOH)3 complexes were evaluated. It was confirmed that the addition of methanol to the aqueous phase (above 25%v/v) causes a synergistic effect.ZusammenfassungDie Bildung des Komplexes von Tm(III) mit 1-(2-Pyridylazo)-2-naphthol (PAN oder HL) in Wasser-Methanol Mischungen (50 und 75%v/v) wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstante für die Reaktion der Komplexbildung und die Stabilitätskonstante des Komplexes TmL2+ wurden berechnet. Die Extraktion von Tm(III) mittelsPAN in Kohlenstofftetrachlorid aus Wasser oder Wasser-Methanol wurde untersucht. Die Werte der Extraktionsgleichgewichtskonstante sowie der zweiphasigen Beständigkeitskonstante für die Komplexe TmL3 und TmL3(MeOH)3 wurden berechnet. Es wurde festgestellt, daß die Zugabe von Methanol zur wäßrigen Phase (∼25%v/v) einen synergistischen Effekt hat.

Complex formation of certain rare earth metals with 1-(2-pyridylazo)-2-naphthol (PAN) in alcohol-water solutions

The formation ofPAN complexes in the systems:Ln(III)—PAN—alcohol—water [whereLn(III) = Pr, Nd, Sm, Eu, Gd, Tb, alcohol - ethanol andLn(III) = Eu, alcohol =n-propanol, isopropanol] was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn3++HL⇌LnL2++H+ (HL =PAN) and stability constants of complexesLnL2+ are reported.ZusammenfassungDie Bildung der Komplexe vonPAN in den SystemenLn(III)—PAN—Alkohol—Wasser [Ln(III) = Pr, Nd, Sm, Eu, Gd, Tb, Alkohol = Ethanol undLn(III) = Eu, Alkohol =n-Propanol, Isopropanol] wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstanten der ReaktionenLn3++HL⇌LnL2++H+ (HL =PAN) und die Stabilitätskonstanten der KomplexeLnL2+ wurden berechnet.

Thermal and Some other Properties of 2,4′-Bipyridyl Complexes with Various Salts of Lead(II)

New complexes of lead(II) with 2,4′-bipyridyl (L), with the general formulae PbL2X2 (where X−1=Cl, Br, I, NCS) and PbL3X2 (where (X]−1=NO3, ClO4), have been prepared. Analysis of the IR spectra indicates that the 2,4′-bipyridyl is bonded to the Pb(II) ion through the least hindering N(4′). The thermal decompositions of the complexes were studied under non-isothermal conditions in air. The intermediates of decomposition at different temperatures were characterized by thermal analysis (TG and DTG), chemical analysis and X-ray diffraction. Upon heating, the complexes undergo full or partial deamination. The complexes PbL2Cl2 and PbL2Br2 decompose to volatile lead(II) halide. PbO is the final product of decomposition for the other complexes.