Spectrophotometric study of thiocyanato complexation of cobalt(II) and nickel(II) ions in micellar solutions of a nonionic surfactant triton X-100

Complexation of cobalt(II) and nickel(II) with thiocyanate ions has been studied by precise spectrophotometry in aqueous and micellar solutions of a nonionic surfactant Triton X-100 of varying concentrations (20–100 mmol-dm^–3). With regard to cobalt(II), the formation of [Co(NCS)]⁺, [Co(NCS)₂], and [Co(NCS)₄]^2– was established. The formation constant of [Co(NCS)₄]^2–, is increased with increasing concentration of the surfactant, suggesting that the [Co(NCS)₄]^2– complex is formed in micelles. In contrast, the formation constants of [Co(NCS)]⁺ and [Co(NCS)₂] are remained practically unchanged. On the other hand, with nickel(II), the formation of sole [Ni(NCS)]⁺ and [Ni(NCS)₂] was established in both aqueous and micellar solutions examined, their formation constants being also remained unchanged. Interestingly, no higher complex was confirmed in the nickel(II) system, unlike cobalt(II). The unusual affinity of the [Co(NCS)₄]^2– complex with micelles will be discussed from thermodynamic and structural points of view.     

Kinetics of ammoniation of some halobis(ethylenediamine)-rhodium(III) perchlorates in liquid ammonia

Summary The ammoniation ofcis-[Rh(en)₂Cl₂] · (ClO₄) in liquid NH₃ was studied at constant ionic medium of 0.20 m perchlorate in the 0 to 35° range. The complex reacts in two distinct steps to givecis-[Rh(en)₂(NH₃)₂] · (ClO₄)₃, with the intermediate formation ofcis-[Rh(en)₂(NH₃)Cl] · (ClO₄)₂. Both steps follow a conjugate-base mechanism. Activation parameters were obtained for the acid-base preequilibrium and the rate-determining step. The entropies of activation for the rate-determining step are 0 and –42 JK^–1mol^–1 for the first and second ammoniations respectively. These values are considerably lower than those found for the cobalt(III) analogues. The entropy changes for the acid-base equilibria are –84 and –36 JK^–1mol^–1 respectively, which is less negative than those values found for the cobalt(III) analogues. Trans-[Rh(en)₂I₂] · (ClO₄) ammoniates totrans-[Rh(en)₂(NH₃)I] · (ClO₄)₂. The contribution of spontaneous ammoniation to the overall reaction oftrans-[Rh(en)₂I₂] · (ClO₄) is negligible, so the uniqueness oftrans-[Co(en)₂Cl₂] · (ClO₄) among cobalt(III) complexes in this respect is not reproduced for thetrans-dihalotetraamine structure in rhodium(III) complexes. A comparison of cobalt(III) and rhodium(III) amines with respect to activation parameters and the influence of formal charge of the metal complex on reactivity indicates a more associative type of activation for rhodium(III).     

Salt and medium effects in the aquation ofcis-amminebromobis(ethylenediamine)cobalt(III) ion

Summary The aquation kinetics ofcis-[Co(NH₃)Br(en)₂]²⁺ were studied in aqueous and mixed aqueous-nonaqueous solvents in the presence of KBr, KCl, LiCl, NaNO₃ and NaClO₄ as supporting electrolytes. It was found that the association between the complex ion and Cl^–, Br^– and NO ₃ ^– ions takes place. The association constants, K_IP, were evaluated from kinetic measurements. The kinetic parameters in the studied media are related to the influence of the cosolvents on the solvation spheres of the reactants and activated complex.     

Coordination compounds of Co(II), Ni(II) and Cu(II) with capric acid hydrazide

The reaction of aquo-ethanolic solutions of Co(II), Ni(II) and Cu(II) salts and ethanolic solution of capric acid hydrazide (L) yielded paramagnetic, high-spin bis- and tris(ligand) chelate complexes. The tris(ligand) complexes, [ML ₃]X ₂·nH₂O [M=Co(II), Ni(II);X=NO ₃ ^– , ClO ₄ ^– , 1/2SO ₄ ^2– ], have an octahedral structure formed on account of the bidentate (NO) coordination of three neutral hydrazide molecules. In the bis(ligand) complexes,ML ₂(NCS)₂ [M=Co(II), Ni(II)] and CuL ₂ X ₂·nH₂O (X=NO ₃ ^– , ClO ₄ ^– and 1/2SO ₄ ^2– ), the oxoanions and NCS^– take also part in coordination. The complexes have been characterized by elemental analysis, IR spectra, magnetic measurements, molar conductivity and TG analysis.

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Caprinsäurehydrazid-Komplexe von Co(II), Ni(II) und Cu(II)

Zusammenfassung Durch die Reaktion von wäßrig-ethanolischen Lösungen von Co(II)-, Ni(II)-und Cu(II)-Salzen mit einer ethanolischen Lösung von Caprinsäurehydrazid (L) wurden paramagnetische high-spin Bis- und Tris-Ligand-Chelatkomplexe erhalten. Tris-Ligand-Komplexe des Typs [ML ₃ X ₂·nH₂O [M=Co(II), Ni(II);X=NO ₃ ^– , ClO ₄ ^– , 1/2SO ₄ ^2– ], die eine oktaedrische Struktur besitzen, entstehen durch die Koordination von drei neutralen zweizähnigen (NO)-Hydrazidmolekülen. Bei den Bis-Ligand-KomplexenML ₂(NCS)₂ [M=Co(II), Ni(II)], sowie bei den Bis-Ligand-Komplexen CuL ₂ X ₂·nH₂O (X=NO ₃ ^– , ClO ₄ ^– , 1/2SO ₄ ^2– ) nehmen bei der Koordination außer Hydrazid auch die Säurereste teil. Die Komplexe wurden durch Elementaranalyse, IR-Spektren, magnetische Messungen, molare Leitfähigkeit und TG-Analysen charakterisiert.

     

Interactions Between Tetra(trifluoromethylsulfonyl)-1,4,8,11-tetraazocyclotetradecane and Perchlorate Anion in Propylene Carbonate, Nitromethane, Acetonitrile, and Tetrahydrofuran

Electrical conductance measurements are reported for lithium perchlorate andthe anion receptor tetra(trifluoromethylsulfonyl)-1,4,8,11-tetraazocyclotetradecane(TTCD) in different aprotic solvents (propylene carbonate, nitromethane,acetonitrile, and tetrahydrofuran). The data have been analyzed by a suitablemethod based on the Lee-Wheaton theory on mixed electrolytes in order to obtainthe true thermodynamic formation constants of macrocyclic-anion complexes andthe ion pairs of both the uncomplexed (ClO₄ ^–)and complexed (TTCD-ClO₄ ^–)anions. The results show that the anion-ligand formation constants increase withdecreasing dielectric constant and that the presence of the ligand increases theionization of lithium perchlorate and enhances the transference number of lithiumion. These findings are of particular interest in view of the technologicalapplication of anion receptors in electrolyte solutions for lithium batteries.     

Activity and Osmotic Coefficients from the Emf of Liquid Membrane Cells. X. Tris(Ethylenediamine) Cobalt(III) Nitrate, Perchlorate, and Chloride

Activity coefficients of [Co(en)₃](NO₃)₃ and [Co(en)₃](ClO₄)₃, to be compared with [Co(en)₃]Cl₃ and the corresponding lanthanum salts previously studied, are determined. [Co(en)₃]Cl₃ data are revised. Ion interaction strengths vary in the same order found for La³⁺, i.e., as if nitrate and perchlorate ions were of smaller and larger size, respectively, than chloride ions; however, the differences are much smaller than in lanthanum salts. Tris(ethylenediamine)cobalt III and lanthanum nitrate, chloride, and perchlorate—like the corresponding hexacyanoferrate(III) and hexacyanocobaltate(III) salts, but contrary to sulfate salts—behave as if [Co(en)₃]³⁺ were smaller in size than La³⁺. In the dilute regions, [Co(en)₃](NO₃)₃ displays negative deviations from the limiting slope, a kind of behavior typical for 2:2, 2:3, 3:2, and 3:3 electrolytes, but unnoticed earlier for 3:1 or 1:3 electrolytes. Pitzer's equation parameters able to provide accurate activity and osmotic coefficients for [Co(en)₃](NO₃)₃, [Co(en)₃](ClO₄)₃, and, revised, [Co(en)₃]Cl₃ are reported.     

Thermodynamics of complexation of zinc(II) with chloride,bromide and iodide ions in hexamethylphosphoric triamide

The complexation of zinc(II) with chloride, bromide and iodide ions has been studied by calorimetry in hexamethylphosphoric triamide (HMPA) containing 0.1 mol-dm^–3 (n-C₄H₉)₄NClO₄ as a constant ionic medium at 25°C. The formation of [ZnX_n]^(2–n)+ (n=1,2,3,4 for X=Cl; n=1,2 for X=Br, I) is revealed, and their formation constants, enthalpies and entropies were determined. It is proposed that the zinc(II) ion is fourcoordinated in HMPA and the coordinating HMPA molecules are stepwise replaced with halide ions to form [ZnX_n(hmpa)_4–n]^(2–n)+ (n=1–4), as is the case for the cobalt(II) ion. Furthermore, the formation of [ZnClI], [ZnBrI], [ZnBrCl] and [ZnBrCl₂]^– is revealed in the relevant ternary systems. It is found that the affinity of a given halide ion X^– to [ZnCl]⁺, [ZnBr]⁺ and [Znl]⁺ is practically the same.     

Electromigration of carrier-free radionuclides

Dependences of La(III) overall ion mobilities on concentrations of ox^2– and tart^2– anions of oxalic and tartaric acid in aqueous solutions of 0.01 overall ionic strength and temperature 298.1 K were obtained by direct measurements of electromigration of carrierfree¹⁴⁰La-lanthanum(III). Concentration stability constants K_n and individual ion mobilities u _i ^o of oxalate and tartrate complexes of La(III) have been calculated for nitrate and perchlorate electrolytes, respectively: [La(ox)]⁺, lg K₁=5.63(9), u⁰[La(ox)]⁺=1.95(15)·10^–4 cm²·s^–1·V^–1; [la(ox)₂]^–, lg K₂=4.05(19) u⁰[La(ox)₂]^–=–1.76(20)·10^–4 cm²·s^–1·V^–1; [La(tart)]⁺, lg K₁=4.40(5), u⁰[La(tart)]⁺=+1.99(18)·10^–4 cm²·s^–1·V^–1.Results are compared with literature data. Additional, limiting individual La³⁺ ion mobility was calculated: =+6.9(1)·10^–4 cm²·s^–1·V^–1 for pure water at 298.1 K.     

Synthesis and Spectroscopic Studies of Chosen Heteropolytungstates and Their Ln(III) Complexes

The heteropolytungstates [(Na)P₅W₃₀O₁₁₀]^4– (I), [(Na)Sb₉W₂₁O₈₆]^18– (II) and [(Na)As₄W₄₀O₁₄₀]^27– (III) and the monovacant Keggin structure of the general formula [XW_11–xMo_xO₃₉]^n– (X-Si, P; n = 7 for P and 8 for Si) (IV) as well as their europium(III) complexes were studied. The structures of I–IV as well as the europium(III) encrypted [(Eu)P₅W₃₀O₁₁₀]^12– (VI), [(Eu)Sb₉W₂₁O₈₆]^16– (VII), [(Eu)As₄W₄₀O₁₄₀]^25– (VIII) and sandwiched [Eu(XW_11–xMo_xO₃₉)₂]^n– (n =11 for P and n = 13 for Si) (V) complexes were synthesized and spectroscopically characterized. The complexes were studied using UV-Vis absorption and luminescence, as well as the laser-induced europium ion luminescence spectroscopy. Absorption spectra of Nd(III) were used to characterize the complexes formed. Excitation and emission spectra of Eu(III) were obtained for solid complexes and their solutions. The relative luminescence intensities of the Eu(III) ion, expressed as the ratio of the two strongest lines at 594 nm and 615 nm, = I₆₁₅/I₅₉₄, which is sensitive to the environment of the primary coordination sphere about the Eu(III) ion, was calculated. In the case of the sandwiched [Eu(XW_11–xMo_xO₃₉)₂]^n– complexes a linear dependence of the luminescence quantum yield of Eu(III) ion, , (calculated using [Ru(bpy)₃]Cl₂ as a standard) on the content of Mo (number of atoms, x) in the [Eu(XW_11–xMo_xO₃₉)₂]^n– structure was observed.     

Solute-solvent interactions with metal chelate electrolytes. Part III. Salting in of tris(acetylacetonato)cobalt(III) and benzene by aromatic and aliphatic ions

Salting effects of the metal chelate electrolytes, [Fe(phen)₃]Br₂, [Fe(bpy)₃]Br₂, [Co(phen)₃]Br₃, [Co(en)₃]Br₃, and [Co(pn)₃]Br₃ (where phen= 1,10-phenanthroline, bpy=2,2-bipridyl, en=ethylenediamine, and pn=1,2-propanediamine), as well as the tetraalkylammonium bromides (Bu₄NBr and Pr₄NBr), tetraphenylphosphonium bromide (Ph₄PBr), sodium tetraphenylborate (NaBPh₄), and sodium halides on the solubility of benzene and tris(acetylacetonato) cobalt (III) [Co(acac)₃, where acac=CH₃·CO·CH·CO·CH₃-] in water at 15, 20, 25, and 35°C were studied, and the transfer free energies of the nonelectrolytes from pure water to the electrolyte solutions were obtained. Co(acac)₃ is strongly salted in by [Fe(phen)₃]Br₂, NaBPh₄, and Ph₄PBr with large positive transfer enthalpies and entropies, weakly salted in by Bu₄NBr and Pr₄NBr with much less positive enthalpies and entropies and is salted out by the other electrolytes. The differences between salting effects of aromatic and aliphatic ions are discussed using the transfer enthalpy-entropy relation.     

Volumetric properties of dilute aqueous solutions of cobalt amine type salts. Part 2. Densities at 15 and 5°C

Apparent molar volumes have been determined by density measurements of aqueous solutions for a series of salts [Co(L)₃]X₃, where X=Cl^– and Br^– and L¹=1,2-diaminoethane (en), L²=1,2-diaminopropane (pn) and L³=1,3-diaminopropane (tn) at 15°C and 5°C. Apparent molar volumes at infinite dilution for the complex cations at 0°C are estimated. The resulting values are related to the structure of solvent water molecules around the ions.     

Synergistic extraction of cobalt(II) with oxine/decanoic acid solution mixtures in benzene and chloroform

Synergistic extraction of Co(II) with 8-hydroxyquinoline (Hq)/decanoic acid [(HR)₂] solution mixtures in benzene and chloroform was carried out at 25°C. The aqueous ionic strength and the total concentration of cobalt(II) were 0.1 (NaCl) and 1·10^–5–1·10^–3M, respectively. The synergistic effect is interpreted by the formation of the mixed ligand ion-pair complexes: [(Coq(Hq)₂(HR))⁺, R^–] and [(Coq(Hq)₂(HR)₃)⁺, R^–] in benzene and chloroform, respectively.     

Thermal and photochemical interaction of octacyanometallates(IV), [M(CN)8]4− (M = Mo or W) in the presence of pyrazine

The interactions between [M(CN)₈]^4– (M = Mo or W) and pyrazine (pz) in the solid state and in aqueous solutions have been analysed. In strongly acidic solutions {pzH⁺, [M(CN)₈]^4–} ion pair formation is observed; the pyrazinium salts (pzH)₂(H₃O)₂[Mo(CN)₈]·0.5pz·3H₂O and (pzH)₂K(H₃O)[W(CN)₈]·H₂O have been isolated. The X-ray crystal structure of the latter, and the spectroscopic properties of both, are described. The [W(CN)₈]^4– anion is approximately square antiprismatic (D_4d), with different H-bond environments around the N atoms. The ligand-field photolysis of [M(CN)₈]^4– in the presence of pyrazine in neutral and alkaline solution results in the formation of tetracyanooxometallates(IV) in equilibrium with pentacyanooxometallates(IV) through the [M(CN)₇(pz)]^3– anions as intermediates. The formation of the [M(CN)₆(pz)₂]^2– ion, postulated in the literature to be the final product of the alkaline photolysis, has definitively been excluded.     

Bacterial activity of cobalt(III) complexes. Part IV: Diethylenetriaminemonoacetatocobalt(III) complexes

Summary The activities of the diethylenetriaminemonoacetatocobalt(III) complexes, [Co(en)(DTMA)]I₂, [CoX₂(DTMA)] and [CoCO₃(DTMA)]·H₂O (DTMA=diethylenetriaminemonoacetato or formally 3-amino-3, 6-diazaoctanato; en=ethylenediamine, X=Cl^–, NO ₂ ^– , NCS^–) were studied onEscherichia coli B growing in a minimal glucose medium in both lag- and log-phases. Activities decrease in the order: [Co(NCS)₂(DTMA)]> [Co(NO₂)₂(DTMA)]>[Co(en)(DTMA)]I₂>[CoCl₂(DTMA)] >[CoCO₃(DTMA)]·H₂O. The antagonistic activities of the complexes were also studied.     

Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

Reactions of carbonate (CO ₃ ^–· ) and bicarbonate (HCO ₃ ^· ) radicals generated by photolysis of a carbonate or bicarbonate solution at pH 11.2 and 8.5, respectively, with Co(II) complexes of iminodiacetic acid (IDA) and ethylenediaminetetraacetic acid (EDTA) have been studied. The rate constants for the reactions were in the order of 10⁶–10⁷ dm³mol^–1s^–1. From the time-resolved spectroscopy of the products formed after reaction of CO _3· ^–· or HCO ₃ ^· , it is observed that CO ₃ ^–· or HCO ₃ ^· oxidize the metal center to its higher oxidation state.     

Volumetric properties of dilute aqueous solutions of cobalt-amine-type salts. Part I. Densities at 25°C

The densities of dilute aqueous solutions of [CoL₃]X₃ [L=1,2-diaminoethane(en), 1,2-diaminopropane(pn), 1,3-diaminopropane(tn) X=Cl^–, Br^– and (ClO₄)^–] have been measured at 25°C from 0 to 5×10^–2m. The apparent molar volumes were calculated and extrapolated to infinite dilution. Ion-solvent interactions were detected from the change of the ionic partial molar volumes with concentration. These interactions depend both on the properties of the ion (polarization charge density at the surface, hydrophobic groups, etc.) and the characteristics and structure of the solvent.     

Osmotic coefficients of dilute aqueous solutions of unsymmetrical cobalt-amine type salts at 0°C

The osmotic coefficients of dilute aqueous solutions of [Co(pn)₃]X₃ [pn=1,2-diaminopropane and X=Cl^–, Br^– and (NO₃)^–] and [Co(tn)₃]X₃ (tn=1,3-diaminopropane and X=Cl^– and Br^–) have been measured from 0.00 to 0.02 mol-kg^–1 at 0°C by the freezing point method. The results have been compared with those obtained from the numerical integration of the Poisson-Boltzmann equation.     

Solubilities and Gibbs transfer energies of thiolato,sulfenato, sulfinato and tris(ethylenediamine)cobalt(III) complexes,as well as of perchlorate,from acetonitrile into its mixtures with water

Information on the solvation of thiolato complex cations [Co(en)₂(SCH₂COO)]⁺ [Co(en)₂(SCH₂CH(COO)NH₂)]⁺, [Co(en)₂(SCH₂CH₂NH₂)]²⁺, sulfenato complexes [Co(en)₂(SOCH₂COO)]⁺ [Co(en)₂{SOCH₂CH(COO)NH₂}]⁺, [Co(en)₂(SOCH₂CH₂NH₂)]²⁺, the sulfinato [Co(en)₂{SO₂CH₂CH(COO)NH₂}]⁺, [Co(en)₂(SO₂CH₂CH₂NH₂)]²⁺ as well as of [Co(en)₃]³⁺ has been obtained from solubility measurements in MeCN–H₂O mixtures at 298.2 K. The single-ion Gibbs energies of transfer of the Co^III complexes were derived from the solubilities of picrate and perchlorate salts for the full range of MeCN–H₂O mixtures. Single-ion Gibbs energies of transfer for the perchlorate ion are given. The effects of the solvent mixtures were interpreted in the framework of chemical bond formation between the ions and the individual solvent molecules.     

Sulfito- und Thiosulfato-Komplexe des Kobalts(III) mitα-Benzildioxim Überα-Dioximinkomplexe der Übergangsmetalle, 52. Mitt.

Some new ligand exchange reactions of [Co(diph·H)₂Cl(H₂O)] and [Co(diph·H)₂(SO₃)(H₂O)]^– complexes with N₃ ^–, S₂O₃ ^2– and with aromatic and heterocyclic amines were carried out. A series of derivatives of the types [Co(diph·H)₂(SO₃)X] ^n– (X=N₃ ^–, S₂O₃ ^2– oramine) and [Co(diph·H)₂(S₂O₃)₂]^3– were described and characterized. Some structural problems are resolved and discussed on the basis of UV and IR spectral data.     

Sedimentation potential of complexes of nitroamminecobalt(III) in aqueous solution at 25°C

Sedimentation potentials (SP) were measured for a series of nitroamminecobalt(III) chlorides in aqueous solution. The magnitudes of the sedimentation potentials varied with the number of NO ₂ ^– ligands in the complexes and a definite positive signal was observed for a neutral complex [Co(NO₂)₃(NH₃)₃]⁰. The division of the partial molar volumes of nitroamminecobalt(III) complexes based on the observed SP values resulted in comparable values of the partial molar volume for the Cl^– ion, suggesting no appreciable hydrolysis nor ionic association occur for these nitroammine-cobalt(III) complexes.