Ammonium ion exchange equilibrium on potassium zinc hexacyanoferrate/II/ K2Zn3[Fe/CN/6]2

Potassium zinc hexacyanoferate/II/ K₂Zn₃[Fe/CN/₆]₂ was prepared and used for the investigation of the uptake of ammonium ion NH ₄ ⁺ . The obtained equilibrium data indicate higher selectivity of ammonium ion relative to potassium ion and much lower relative to cesium ion.     

Magnetochemical Study of some Heteropolytungstates with transition cations (Ni,Zn)

On the basis of the magnetic susceptibility measurements carried out on the potassium and ammonium salts of the 11-tungstonickelozincate anion [H₃NiZnW₁₁O₄₀]^7?, the coordinative environment of the Ni²⁺ ion was elucidated.     

Synthesis,spectral characterization and biological evaluation of novel 1-(2-(4,5-dimethyl-2-phenyl-1H-imidazol-1-yl)ethyl)piperazine derivatives

A simple, highly useful synthesis of 1-(2-(4,5-dimethyl-2-phenyl-1H-imidazol-1-yl)ethyl)piperazine derivatives is achieved by a four component cyclo condensation of diacetyl, aromatic aldehyde, 2-(piperazin-1-yl)ethanamine and ammonium acetate using SO₄²⁻/Y₂O₃ as a catalyst in ethanol. The synthesized compounds were characterized by IR, ¹H and ¹³C NMR and mass spectral studies. All the synthesized compounds were screened for their in vitro antimicrobial studies. Among the newly synthesized compounds 5d, 5e, 5h and 5m showed excellent antibacterial and antifungal activities when compared to the standard drugs.     

Effect of Ammonium Ions on the Electroreduction of Anions at a Mercury Electrode

The effect of ammonium ions on the electroreduction of peroxodisulfate (S₂O^2- ₈) and perbromate (BrO^- ₄) anions is found to be commensurate with that of potassium ions. Ammonium ions accelerate the reduction of iodate (IO^- ₃), bromate (BrO^- ₃), and chromate (CrO^2- ₄) anions in nonbuffered solutions and does not, in buffered ones. In the former case, the effect is connected with the pH change in the near-electrode layer during the reaction and with the participation of ammonium ions in hydrolytic equilibriums, rather than with a simultaneous transfer of ammonium ions and electrons in an elementary act. The conclusions in the literature in favor of a simultaneous transfer of the proton and electron in the proton-consuming reactions of reduction of anions is shown to be ambiguous.     

Conformational Studies of Dibenzo-30-crown-10 Complexes. Syntheses and Crystal Structures of Potassium and Ammonium Hexafluorophosphate Complexes

Abstract

Crown ether complexes formed by the dibenzo–30-crown–10 (DB30C10) with potassium and ammonium hexafluorophosphate have been prepared and their crystal structures have been determined by single crystal X-ray analyses. The potassium complex (compound 1) consists of [K(DB30C10)]⁺ cation and PF₆ ^? anion. Crystals are monoclinic, space group P2/n, with a = 11.9106(3), b = 9.8382(5), c = 14.3062(3) Å, β = 97.581(3)°, V = 1661.7(1) ų, D_c = 1.440 g cm^?3, Z = 4, R = 0.0675 for 2528 unique observed reflections. The potassium atom is coordinated to the ten oxygen atoms of the crown ligand at the distance from 2.859(3) to 2.930(3) Å. The ammonium complex (compound 2) has also 1:1 crown—cation ratio. Crystals are monoclinic, space group P2₁/n, with a = 12.5061(6), b = 19.3724(5), c = 14.2203(9) Å, β = 102.476(5)°, V = 3363.8(3) ų, D_c = 1.501 g cm^?3, Z = 4, R = 0.0677 for 4172 unique observed reflections. The ammonium cation is completely enclosed with crown oxygen atoms forming seven hydrogen bonds. The conformation of previously reported dibenzo-30-crown-10 complexes with potassium salts were investigated using polar coordinate maps.     

Synthesis and characterization of methylpalladium(II) dithiolate complexes of the type [PdMe(SS)(ER3)] (SS = S2CNR 2, S2COEt, S2P(OR)2, S2 PPh2; ER3 = PMePh2, PPh3, AsPh3)

Methylpalladium(II) dithiolate complexes of the type [PdMe(SS)(ER₃] (SS = S₂ CNR₂ (R = Me or Et), S₂COEt, S₂P(OR)₂ (R = Et, ⁿPr, ⁱPr), S₂PPh₂; ER₃ = PMePh₂, PPh₃, AsPh₃) have been synthesized by the reaction of [Pd₂Me₂(μ-Cl)₂(PMePh₂)₂] with sodium/potassium/ammonium salts of the dithio acid or by treatment of [PdMeCl(cod)] with ER₃ followed by sodium/potassium/ammonium salts of the dithio ligand. All the complexes were characterized by elemental analysis, IR and nuclear magnetic resonance (¹H, ³¹P) data.     

Preparation of 1,3-dienyl organotrifluoroborates and their Diels-Alder/cross-coupling reactions

2-BF₃-substituted 1,3-butadienes with potassium and tetrabutyl ammonium counterions have been prepared in gram quantities from chloroprene via a simple synthetic procedure. The potassium salt of this new main group element substituted diene has been characterized by ¹H, ¹³C, ¹¹B, and ¹⁹F NMR and the tetra n-butyl ammonium salt was also characterized by X-ray crystallography. Diels-Alder reactions of these dienes with dienophiles such as ethyl acrylate, methyl vinyl ketone, and N-phenylmaleimide are reported as well as subsequent Pd-catalyzed cross-coupling reactions of those Diels-Alder adducts. 4-Phenyl-2-BF₃-substituted 1,3-diene was prepared by magnesium-halogen exchange from the corresponding 2-bromo and iodo dienes. The 4-phenyl-2-bromo-1,3-butadiene was also characterized by X-ray crystallography. 4-Phenyl-2-BF₃-1,3-butadiene was used in Diels-Alder/cross-coupling reactions and the product of a Diels-Alder reaction with N-phenylmaleimide followed by cross-coupling with 4-bromo-benzonitrile was also characterized by X-ray crystallography.     

Über Chrom(II)-carboxylate und Halogenochromate(II)

Highly pure chromium(II) acetate, was obtained from chromium powder and anhydrous acetic acid in the presence of a small amount of acetylhalide. Cr^II acetate reacts with acetyl halide in anhydrous acetic acid to sesquisolvates like CrCl₂ · 3/2 CH₃COOH. If one equivalent of alkali acetate or an organic nitrogen base is added to solutions of Cr^II acetate in acetyl halide/acetic acid mixtures, trihalochromates(II) are precipitated which are hexagonal in structure, except the ammonium and the potassium salt. With two equivalents of alkali or ammonium acetate tetrachlorochromates(II) of cesium, rubidium and ammonium are precipitated. They are tetragonal in structure (K₂NiF₄ type). Using pyridinium acetate with various mixtures of acetyl bromide and acetic acid, only the solvates (PyH)₃(CrBr₅) · 2CH₃COOH is formed.     

Ion chromatographic determination of common ions at ultratrace levels in Antarctic snow and ice

The simultaneous determination of major impurities present in Antarctic snow and ice at ng g^? (ppb) concentrations by ion chromatography is described. Calibration data are presented for ammonium, sodium, potassium, chloride, nitrate and sulphate ions. Special attention is paid to the different ways of removing field contamination from ice and snow cores and suitable equipment is described. The results provide evidence against the validity of published sets of concentration data for nitrogen-containing compounds (NO^?₃ and NH⁺₄ in Antarctic snow, and demonstrate a crucial contamination problem in the determination of ammonium ions.     

Hot atom chemistry in oxyanion targets,part II1: Recoil behaviour of56Mn in permanganates

Fractional precipitation techniques have been utilized to separate the lower valent and parent forms of⁵⁶Mn in permanganate targets and an attempt is made to study a few aspects of chemical stabilization of recoil⁵⁶Mn in permanganates. Ammonium permanganate, recoil behaviour of which has not been studied previously, is chosen as one of the targets along with the potassium permanganate for initial retention and also for isothermal annealing.⁵⁶Mn initial retentions of about 12% and about 4% are obtained for potassium and ammonium permanganate, respectively, by activation from a Ra–Be neutron source. A usual trend for KMnO₄ and the reduction of recoil fragments by ammonium ions in NH₄MnO₄ are seen through the isothermal annealing study.     

Effect of Ammonium Ions on the Radiation Degradation of Potassium Nitrate

The formation and thermal conversion of paramagnetic centers in -irradiated single crystals of potassium nitrate with an ammonium nitrate impurity was studied by EPR spectroscopy. It was found that the presence of ammonium nitrate decreased the radiation-chemical yield of nitrite ions, which are one of the final radiolysis products of nitrate-containing compounds. An analysis of the results of a study on NO₂ orientation in the KNO₃ crystal lattice with an impurity of NH⁺ ₄ allowed us to propose a mechanism for selective N–O bond rupture in the radiation-stimulated dissociation of the nitrate ion in a potassium nitrate matrix.     

Superionic Conduction in Complex Fluorides of Antimony(III) MnSbxFy (M—Cations of an Alkali Metal, Ammonium, or Thallium, n = 1–3, and x = 1–4)

Methods of ¹⁹F NMR and impedance spectroscopy are used to investigate the internal mobility of fluoride (ammonium) ions and electrophysical characteristics of complex trivalent antimony fluorides MSb₄F₁₃, MSb₃F₁₀, MSb₂F₇, M₂Sb₃F₁₁, M₃Sb₄F₁₅, and MSbF₄ (M is an alkali cation, ammonium, thallium). The ion motion types in the cationic and anionic sublattices of the fluorides are determined at 150–500 K. The polymorphous transformations in the fluorides are usually phase transitions to a superionic state and their high ionic (superionic) conductivity (σ ≥ 10⁻⁴ to 10⁻² S cm⁻¹ at 400 K) is due to the diffusion motion of ions of fluoride, ammonium, and possibly sodium, potassium, and thallium. The high polarizability of thallium ions favors the development of high mobility of fluoride ions in the fluorides.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 560–572.Original Russian Text Copyright © 2005 by Kavun, Uvarov, Slobodyuk, Brovkina, Zemnukhova, Sergienko.     

Mössbauer study of the thermal decomposition of alkali tris(oxalato)ferrates(III)

The thermal decomposition of alkali (Li,Na,K,Cs,NH₄) tris(oxalato)ferrates(III) has been studied at different temperatures up to 700°C using Mössbauer, infrared spectroscopy, and thermogravimetric techniques. The formation of different intermediates has been observed during thermal decomposition. The decomposition in these complexes starts at different temperatures, i.e., at 200°C in the case of lithium, cesium, and ammonium ferrate(III), 250°C in the case of sodium, and 270°C in the case of potassium tris(oxalato)ferrate(III). The intermediates, i.e., Fe¹¹C₂O₄, K₆Fe¹¹₂(ox)₅. and Cs₂Fe¹¹ (ox)₂(H₂O)₂, are formed during thermal decomposition of lithium, potassium, and cesium tris(oxalato)ferrates(III), respectively. In the case of sodium and ammonium tris(oxalato)ferrates(III), the decomposition occurs without reduction to the iron(II) state and leads directly to α-Fe₂O₃.     

Microelectrode for potassium ions based on a neutral carrier and comparison of its characteristics with a cation exchanger sensor

A potassium-selective liquid-membrane microelectrode based on valinomycin is described. Tip diameters of about 2 μm as well as high discrimination against Na⁺, H₃O⁺, acetylcholine and some other quaternary ammonium ions, allow the intracellular measurement of potassium ion activity changes. The inherently high membrane resistance of the neutral carrier-based microelectrodes is reduced by adding a lipophilic charge carrier to the valinomycin. Results are compared with those of classical microelectrodes.     

Potassium hydrogen diphthalate dihydrate: a new structure and correction to the literature

The title compound, K⁺·[(C₈H₅O₄)₂H]⁻·2H₂O or K⁺·C₁₆H₁₁O₈⁻·2H₂O, was prepared by slow evaporation of an aqueous solution of potassium hydrogen phthalate. The molecular complex consists of a potassium cation coordinated to a proton‐bound hydrogen phthalate dimer and two water mol­ecules. The potassium cation resides on a twofold axis in a distorted square‐antiprism coordination geometry. The compound is isomorphous with the ammonium analogue, previously misidentified. As potassium hydrogen phthalate is frequently used in the manufacture of buffers, organic carbon standards, acidimetric standards and various other products, the crystallization of a compound with a different stoichiom­etery from a solution containing the acidimetric standard has important practical implications.     

Vibrational behavior of matrix-isolated ions in Tutton compounds. V. Infrared spectroscopic study of NH4+ and SO42− ions included in zinc sulfates and selenates

Infrared spectra of K₂Zn(SeO₄)₂·6H₂O and (NH₄)₂Zn(SeO₄)₂·6H₂O containing SO₄^2? guest ions and those of K₂Zn(SO₄)₂·6H₂O and K₂Zn(SeO₄)₂·6H₂O containing NH₄⁺ guest ions are presented and discussed in the region of the stretching modes ν₃ and ν₁ of the sulfate ions and in the region of asymmetric bending modes ν₄ of the NH₄⁺ ions, respectively. The SO₄^2? ions matrix-isolated in the selenate matrices (approximately 2 mol%) exhibit three bands for ν₃ and one band for ν₁ in agreement with the low site symmetry C₁ of the selenate host ions. The NH₄⁺ guest ions included in the potassium sulfate matrix are characterized also with three site symmetry components of ν₄. However, the ammonium ions in (NH₄)₂Zn(SeO₄)₂·6H₂O as well as those included in K₂Zn(SeO₄)₂·6H₂O display four infrared bands corresponding to ν₄ probably due to some kind of disorder of the ammonium ions. The extent of energetic distortion of the isomorphously included sulfate ions as deduced from the values of Δν₃ (site-group splitting) and Δν_max (the difference between the highest and the lowest wavenumbered components of the stretching modes) are commented. The spectroscopic experiments reveal that the SO₄^2? guest ions are weaker distorted in the potassium selenate matrix than the same ions in the neat potassium sulfate due to the larger unit-cell volumes of the selenate compounds. However, the SO₄^2? guest ions are stronger distorted in the ammonium selenate matrix as compared to the same ions in the neat ammonium sulfate owing to the formation of hydrogen bonds between the SO₄^2? guest ions and the NH₄⁺ host ions. The analysis of the spectra shows that the band positions of the water librations in the host potassium compounds are affected by the included ammonium cations. The formation of the hydrogen bonds between the NH₄⁺ guest ions and the XO₄^2? host ions leads to a decrease in the proton acceptor capabilities of the anions (anti-cooperative or proton acceptor competitive effect) and as a result the hydrogen bonds formed by the water molecules weaken on going from the neat potassium compounds to the mixed crystals K_1.8(NH₄)_0.2Zn(SO₄)₂·6H₂O and K_1.8(NH₄)_0.2Zn(SeO₄)₂·6H₂O (the bands corresponding to water librations are broadened and shifted to lower frequencies).     

Infrared and Raman spectra of tripotassium dihydrogen triphosphate and its ammonium derivatives

In order to obtain information on the completeness of potassium dihydrogen triphosphate topochemical ammonization the authors have studied the i.r. and Raman spectra of K₃H₂P₃O₁₀·H₂O, products of its interaction with gaseous ammonia and ammonium—potassium triphosphate (K:NH₄ = 3:2) precipitated from aqueous solution. The assignments of the absorption bands (2000-400 cm⁻¹; 293 and 100 K) have been made. The spectra of double salts obtained by different methods, in contrast to their X-ray diffraction patterns, have been found to be identical. This is indicative of the completeness and partial topotaxity of acidic salt topochemical ammonization. The ammonization process can be investigated through the changes in intensity of the bands pertaining to the vibrations of the -PO₃H end group: v_sPO^*₂, vPO(H) and δPO(H).     

Ion Association and Solvation Behavior of Some 1-1 Electrolytes in 2-Ethoxyethanol Probed by a Conductometric Study

Precise measurements of the electrical conductances of solutions of potassium thiocyanate (KCNS), ammonium thiocyanate (NH₄CNS), sodium nitrate (NaNO₃) and ammonium nitrate (NH₄NO₃) in 2-ethoxyethanol (EE) at temperatures 35, 40, 45 and 50,^∘C are reported. The conductance data have been analyzed by the 1978 Fuoss conductance equation. A thermodynamic analysis of the ionic association processes has also been made and the Coulombic forces are found to play a major role in the association processes. The ionic contributions to the limiting equivalent conductances have been determined using the reference electrolyte method. Strong association was found for all these electrolytes in this solvent medium. The cations are found to be substantially solvated in 2-ethoxyethanol, whereas the anions appear to have only weak interaction with the solvent molecules.     

Oxovanadium(V) complexes incorporating tridentate aroylhydrazoneoximes: Synthesis, characterizations and antibacterial activity

Some new oxovanadium(V) complexes, [VOL^1-3(OEt)(EtOH)] (1-3), have been reported, which were obtained from the reaction of the Schiff bases H₂L^1-3 (where H₂L¹ = the salicylhydrazone of diacetyl monoxime; H₂L² = the 4-methoxy salicylhydrazone of diacetyl monoxime and H₂L³ = the 4-hydroxy salicylhydrazone of diacetyl monoxime) with VO(acac)₂ in a 1:1 molar ratio. Three 4-R-aroylhydrazoneoximes (V) have been used as ligands in the present study, differing in the inductive effect of the substituent R (R = H, OCH₃ and OH), in order to observe their influence, if any, on the redox potentials and biological activity of the complexes. All the synthesized ligands and metal complexes were successfully characterized by elemental analysis, IR, UV-Vis and NMR spectroscopy. An X-ray diffraction study of [VOL¹(OEt)(EtOH)] (1) reveals that the metal center has a distorted octahedral O₅N coordination sphere, where the O,N,O donor ligand and the ethoxo group constitute a satisfactory O₃N basal plane. Cyclic voltammetry of the complexes show a quasi-reversible cyclic voltammetric response in the potential range 0.29-0.36 V involving a single electron V(V)-V(IV) reduction. The complexes have also been screened for their antibacterial activity against Escherichia coli, Bacillus, Proteus and Klebsiella. Minimum inhibitory concentrations of these complexes and the antibacterial activities indicate compound 1 as the potential lead molecule for drug design.     

Umsetzungen von Tetrafluor-1,2-ethandisulfenyldichlorid mit Ketonen und Olefinen

Reactions of Tetrafluoro-1, 2-ethanedisulfenyldichloride with Ketones and Olefines The reaction of ClSCF₂CF₂SCl 1 with (CH₃)₃C? C(O)CH₃, hexene, diacetyl, cyclobutanone, and H₂C?CHC(O)CH₃ leads to the cyclic and acyclic products 2 – 6 . They are destillable liquids, which have been characterized on the basis of elemental analysis, mass spectra, ¹⁹F-, ¹³C-, and ¹H-n.m.r. spectra. The reaction mechanism will be discussed.