Reaction of Gelatin-immobilized Lead(II) Hexacyanoferrate(II) with Dithioxamide

Russian Journal of General Chemistry -     

Sorption of Hexacyanoferrate(II,III) Anions on Nickel(II) Hydroxide

Fe(CN)₆ ^{3 -} and Fe(CN)₆ ^{4 -} anions are sorbed from aqueous solutions of their potassium and cesium salts on -Ni(OH)2 by the mechanism of anion exchange with hydroxy groups. Alkali metal cations (K⁺, Cs⁺) are also partly sorbed on nickel(II) hydroxide in the form of anionic complexes (K,Cs) _z Fe(CN)₆ ^{(n - z)-}, where n = 3 or 4 (0 < z < n). The chemical composition of the new phase appearing in contact of nickel(II) hydroxide with aqueous potassium and cesium hexacyanoferrates(II, III) was determined by X-ray phase analysis and IR spectroscopy.     

Lead(II) Sulfide. Synthesis in Lead(II) Tetraoxophosphate(V) Gelatin-immobilized Matrix Implantates and Sorption Activity Toward Silver(I) Ions

Processes that occur in lead(II) tetraoxophosphate(V) gelatin-immobilized matrix systems on their contact with aqueous solutions containing the sulfide anion S₂ ^- were studied. As a result of this contact, lead(II) sulfide is formed. The sorption activity of the resulting metal sulfide gelatin-immobilized matrix systems with respect to Ag(I) ions is associated with substitution of Pb(II) by Ag(I) ions.     

Radiation Effect on Concentrated Potassium Hexacyanoferrate(II) Solutions

Neutron irradiation was carried out on 0.2, 0.4 and 0.7 M solutions of potassium hexacyanoferrate(II) at the pH range of 2-10. Fe(CN)₅^1? was found when pH<5; which is consistent with the oxidation potential consideration of the slow reaction between Fe(CN)₅^4? and OH. Fe(OH), was precipitated in the whole range of pH studied. Chemical and radiochemical yields were compared.     

Synthesis and Characterization of Bis(Macrocyclic) Nickel(II) Complexes Containing Aromatic Nitrogen–Nitrogen Linkers Produced by Template Condensation

Bis(macrocyclic)dinickel(II) complexes containing phenylene bridges between 16-membered pentaaza macrocyclic subunits have been synthesized via one-pot template condensation of nitrogen–nitrogen linker (1,4-phenylenediamine; benzidine; 4,4′-diaminodiphenylmethane; 4,4′-diaminodiphenylether; 4,4′-diaminodiphenylsulfone), formaldehyde, 1,3-diaminopropane, nickel(II) and 2,4-pentanedione in a 1:4:4:2:2 molar ratio. Elemental analyses, i.r., u.v.–vis, H-n.m.r. spectroscopy, cyclic voltametry, conductometric and magnetic measurements have been used to characterize the new complexes.     

Kinetics of the photoaquation of Hexacyanoferrate(II) ion

Kinetics of the photoaquation of hexacyanoferrate(II) ion in aqueous solution were studied potentiometrically and spectrophotometrically. Supposing the simplest mechanism (see Fig. 3. in text), the photoaquation in alkaline medium can be well described. The value of the constants at pH = ll.0 are: ø = 0.8-1.0, k₆ = (3.0 ± 0.5) × 10^?8 s^?1 and k_?6 = 1.5 ± 0.2 mol^?1 dm₃ s^?1. To describe the photoaquation in neutral medium t was extended (k′ = 3.33 x 10² mol^?1 dm³s^?1). The quantum yield in acidic medium can be calculated by combination of ø values of different protonated complexes. The reversibility of photoaquation in alkaline medium is also explained by the scheme.     

Synthesis and properties of one-dimensional Ni(II) and Ni(II)Cu(II) complexes linked by hydrogen bond

Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me₆[14]dieneN₄)Ni₂(Dto)₂) (1), (Me₆[14]dieneN₄)CuNi(Dto)₂ (2), (Me₆[14]aneN₄)Ni₂(Dto)₂ (3), and (Me₆[14]aneN₄)CuNi(Dto)₂ (4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2. 2425(4) nm,b = 1.0088(2) nm,c= 1.4665(3) nm, β= 125.32(3)δ Z = 4;R = 0.076, R_w = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of macrocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.     

Electrophilic Copper(II) → Metal(II) Substitution in Gelatin-Immobilized Copper(II) Hexacyanoferrate(II) Matrix Implants

Contact of thin layers of gelatin-immobilized copper(II) hexacyanoferrate(II) matrices with aqueous solutions of Co(II), Ni(II), Zn(II), and Cd(II) chlorides results in partial substitution of these ions for Cu(II) to give (dd)-heterobinuclear hexacyanoferrates(II) of copper(II) and the corresponding double-charged ion.     

Nickel(II) aminoalkoxides

Summary Nickel alkoxides react with mono-, di- and tri-ethanolamines in different stoichiometric ratios and novel products have been isolated and characterized by elemental analyses, i.r. and electronic reflectance spectra. Insertions across the Ni-O bond in aminoalkoxides have been studied for the first time.     

Solvent-Free Synthesis of Arylsulfonyl Cyanides Using Potassium Hexacyanoferrate(II) as An Ecofriendly Cyanide Source

Abstract

A solvent-free synthetic method for arylsulfonyl cyanides directly from corresponding sulfonyl chlorides using potassium hexacyanoferrate(II) as an ecofriendly cyanide source is described. The protocol has the advantages of no uses of highly toxic cyanating agent and volatile organic solvents, high yield, and simple work-up procedures.     

Immobilization of Silver(I) Hexacyanoferrate(II) in Thin Gelatin Layers

Russian Journal of General Chemistry -     

Decontamination of Radioactive Liquid Waste with Hexacyanoferrate(II)

Concerning decontamination of a radioactive liquid waste which includes seawater and nuclides from irradiated fuels and activated materials, the in-situ generation of metal hexacyanoferrates(II) by adding potassium hexacyanoferrate(II) and codecontamination of ^134,137Cs and some activation products were investigated. Transition metals arising from seawater in the waste solution precipitates in the preference order of Zn>Ni≥Co>Mn according to their solubility. The precipitate adsorbs ^134,137Cs, and decontamination will be attained by the following sedimentation with a polymer and filtration, as an example. Decontamination factor of activated products, ⁶⁰Co and ⁵⁴Mn, is dependent on concentration of hexacyanoferrate(II) in the solution.     

Template synthesis and physicochemical studies of 14-membered hexaazmacrocyclic complexes with Co(II), Ni(II), Cu(II) and Zn(II): a comparative spectroscopic approach on DNA binding with Cu(II) and Ni(II) complexes

A new series of 14-membered pendant arm hexaazamacrocyclic complexes of the type [MLX₂] · [M = Co(II), Ni(II), Cu(II) or Zn(II) for X = Cl; Co(II), Ni(II), Cu(II) or Zn(II) for X = NO₃] has been synthesized by metal template condensation of 1,2-phenylenediamine and 1,4-phenylenediamine with formaldehyde in methanol. The mode of bonding and overall geometry of these complexes have been deduced by elemental analyses, molar conductance values, FT-IR, ¹H-NMR, ¹³C-NMR, EPR, ESI-mass and UV–VIS along with magnetic measurement studies. The fluorescence and UV–VIS studies revealed a significant binding ability to DNA.     

Mild Template Synthesis of (2,8-Dithio-3,7-diaza-4,6-dimethyl-5-oxanonanedithioamido-1,9)copper(II) in Cu2[Fe(CN)6] Gelatin-Immobilized Matrices

Complexation process in Cu₂[(Fe(CN)₆] gelatin-immobilized matrices in contact with aqueous solutions of dithiooxamide H₂N–C(S)–C(S)–NH₂ and ethanal H₃C–CHO at pH > 10 were studied. The template synthesis was shown to occur under these specific conditions to yield the Cu(II) chelate with tetradentate (N,N,S,S)-ligand (2,8-dithio-3,7-diaza-4,6-dimethyl-5-oxanonanedithioamide-1,9) with a metal : ligand ratio of 1 : 1. Dithiooxamide and ethanal therein act as ligand syntones. The reaction scheme was suggested. It was established that this tetradentate ligand is not formed in the absence of Cu(II) in a solution in contact with the matrix. Moreover, the attempts made to obtain the title compound through the reactions of known copper(II) dithiooxamide complexes with ethanal failed.     

The Solid State Electrochemistry of Dysprosium(III) Hexacyanoferrate(II)

A new electroactive polynuclear inorganic compound of rare earth metal hexacyanoferrate, dysprosium hexacyanoferrate (DyHCF), was prepared chemically and characterized using techniques of FTIR spectroscopy, thermogravimetric analysis (TGA), UV‐vis spectrometry and X‐ray photoelectron spectroscopy (XPS) etc. The cyclic voltammetric behavior of DyHCF mechanically attached to the surface of graphite electrode was well defined and exhibited a pair of redox peaks with the formal potential of 217 mV (vs. SCE) at a scan rate of 100 mV/s in 0.2 M NaCl solution and the redox peak currents increased linearly with the square root of the scan rates.