Synthesis of certain pyridinyl and diazinyl hydrazones containing one or more ferroin groups, and their chromogenic reactions with iron, copper, cobalt and nickel

Fifteen new hydrazones with one or more ferroin groups were prepared, and their chelation and chromogenic properties with iron(II), copper(I), cobalt(II) and nickel(II) were investigated. Improved sensitivity in the spectrophotometric determination of cobalt, copper, and nickel is provided by several of the new compounds. Several others are capable of forming unusually stable and interesting binuclear iron(II) complexes.     

Microdetermination of Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd, Hg, Pb, Bi and U in inorganic and organometallic compounds with morpholinium morpholine-N-dithiocarboxylate

The chelates of morpholinium morpholine-N-dithiocarboxylate with manganese(II), iron(II), iron(III), cobalt(II), nickel, copper(II), zinc, silver, cadmium, mercury(II), lead, bismuth and uranium(VI) have been prepared and their compositions elucidated. Simple, accurate and relatively rapid procedures for the gravimetric and titrimetric microdetermination of these metals in inorganic and organometallic compounds are presented.     

New chromogens of the ferroin type-IX 2-pyridyl and pyrazinylhydrazones of some pyridyl, pyrazinyl and pyridazinyl ketones and of isatin and phenylglyoxal

Chromogenic properties of 22 new hydrazones, all ferroin-type compounds, have been evaluated with respect to iron(II), copper(I), cobalt(II) and nickel(II). Some show promise as sensitive reagents for the determination of trace amounts of these metal ions. Stoichiometric ratios were determined for the iron(II) chelates and interpreted to distinguish between syn- and anti-isomers.     

New chromogens of the ferroin type-VIII Some di- and trisubstituted 1,2,4-triazines, 3-substituted-9H-indeno[1,2-e]-1,2,4-triazin-9-ones, and di- and trisubstituted 1,2,4-triazolines

Thirty-six new ferroin compounds have been investigated as possible chelation regents for the calorimetric detection and determination of trace amounts of iron(II), copper(I), and cobalt(II). Spectral data, solution conditions favourable for chelate formation, and other data are reported. The results reveal that incorporation of triazoline heterocycles in ferroin chromophore groupings generally leads to poor chromogenic properties, except with respect to cobalt. Triazine groups, however, can give rise to superior properties. The most sensitive iron(II) chromogen of the ferroin type found to date and a promising new cobalt chromogen are described.     

New chromogens of the ferroin type-VII Some 3-substituted-1,2,4-triazines, 3,5-disubstituted-1,2,4-triazolines and triazoles, and 2,4- and 2,6-bis triazinyl and triazolinyl substituted pyridines

Chelation and chromogenic properties of 39 new ferroin compounds in reactions with iron(II), copper(I), and cobalt(II) have been investigated spectrophotometrically. The results demonstrate that the chromogenic properties of triazole and triazoline heterocycles are inferior to triazine and pyridine when incorporated into the ferroin chromophore grouping. The triazole and triazoline compounds also undergo hydrolytic decomposition, strongly catalysed by iron(II), making them unsuitable as colorimetric reagents. An outstanding chromogen was found from among the triazine derivatives which is superior in sensitivity to all ferroin-type chromogens previously studied.     

Structure,insertion electrochemistry,and magnetic properties of a new type of substitutional solid solutions of copper,nickel, and iron hexacyanoferrates/hexacyanocobaltates

Substitutional solid solutions of metal hexacyanometalates in which low-spin iron(III) and cobalt(III) ions populate the carbon-coordinated sites were synthesized and studied by powder diffraction including Rietveld refinement, cyclic voltammetry of immobilized microparticles, diffuse reflection vis-spectrometry, and magnetization techniques. The continuous solid solution series of potassium copper(II), potassium nickel(II), and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] show that the substitution of low-spin iron(III) by cobalt(III) in the hexacyanometalate units more strongly affects the formal potentials of the nitrogen-coordinated copper(II) and high-spin iron(III) ions than those of the remaining low-spin iron(III) ions. In the case of copper(II) and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] the peak currents decrease much more than can be explained by stoichiometry, indicating that the charge propagation is slowed by the substitution of low-spin iron(III) by cobalt(III). The Rietveld refinement of all compounds confirmed the structure initially proposed by Keggin for Prussian blue and contradicts the structure described later by Ludi. The dependencies of lattice parameters on composition exhibit in all series of solid solutions studied similar, although small, deviations from ideality, which correlate with the electrochemical behavior. Finally, a series of solid solutions of the composition KNi(0.5)(II)Cu(0.5)(II)[Fe(III)(CN)(6)](1-x)[Co(III)(CN)(6)](x), where both the nitrogen- and carbon-coordinated metal ions are mixed populated and were synthesized and characterized. These are the first examples of solid solutions of metal hexacyanometalates with four different metal ions, where both the nitrogen- and the carbon-coordinated sites possess a mixed population.     

Reaction of 3d-transition metal nicotinates and isonicotinates with thiosemicarbazide

Reaction of iron(II), cobalt(II), nickel(II), and copper(II) nicotinates and isonicotinates with thiosemicarbazide were studied, and the resulting coordination compounds were characterized by elemental analyses, IR spectra, diffuse reflectance spectra, and thermogravimetric data.     

New chromogens of the ferroin type-X synthesis and chelation properties of some 2-thiazolyl- and 2-pyrimidinylhydrazones

Preparation of some new hydrazones which possess the ferroin chromophoric group is described, together with results of spectrophotometric studies of their chelation reactions with iron(II), copper(I), cobalt(II) and nickel(II). Several of the new compounds show promise as highly sensitive chromogenic reagents for simultaneous determinations of these metals.     

Synthesis and metallochromic properties of some new mono- and bishydrazones of benzil and 2,2'-pyridil

Preparation of some new mono- and bishydrazones which possess the ferroin chromophoric group is described, together with results of spectrophotometric studies of their chelation reactions with iron(II), copper(I), cobalt(II), nickel(II) and zinc(II). Several of the new compounds show promise as chromogenic reagents for these metals. The results are also of interest with regard to structure-reaction relationships.     

Simultaneous determination of cobalt,copper, iron and vanadium in crude petroleum oils by HPLC

Summary A method has been developed for the simultaneous formation and solvent extraction of cobalt (II), copper (II), iron (II) and vanadium (IV) complexes of bis (acetylpivalylmethane)ethylenediamine (H₂APM₂en) in methyl isobutyl ketone. The complexes are eluted from a reversed phase HPLC column with a mixture of methanol:water:acetonitrile and detection was at 260 nm. The method has been applied to the simultaneous determination of cobalt, copper, iron and vanadium in crude petroleum oils at the ng level.     

Coordination compounds of 3d-metals salicylates with thiosemicarbazide

Complexes of copper(II), nickel(II), cobalt(III), zinc(II), and iron(III) salicylates with thiosemicarbazide were synthesized. The resulting compounds were characterized by the elemental analysis data, infrared spectroscopy, diffuse reflectance spectroscopy, and thermogravimetry.     

Coordinational compounds of 3<Emphasis Type="Italic">d</Emphasis>-metal phthalates with nicotinamide

Complexes of iron(II), cobalt(II), nickel(II), copper(II), and zinc with nicotinamide were synthesized. The compounds obtained were characterized by means of chemical analysis, conductometry, thermogravimetry, and by means of the IR and the diffuse reflection spectroscopy.     

Iron(II), cobalt(III), nickel(II) and copper(II) chelates of furan and thiophene azo-oximes

Summary Complexes of furan and thiophene azo-oximes with iron(II), cobalt(III), nickel(II) and copper(II) have been prepared and characterised. Iron(II), cobalt(III) and copper(II) complexes are diamagnetic in the solid state. The diamagnetism of the copper(II) chelates is suggestive of antiferromagnetic interaction between two copper centres.¹H n.m.r. spectral data suggest atrans-octahedral geometry for the tris-chelates of cobalt(III). Nickel(II) complexes are paramagnetic, in contrast to the diamagnetism of the analogous complexes of arylazooximes. The electronic spectra are suggestive of octahedral geometry for the iron(II), cobalt(III) and nickel(II) complexes, andD _4h -symmetry for copper(II). Infrared data indicate N-bonding of the oximino-group to the metal ions.     

Liquid chromatographic determination of cobalt(II), copper(II) and iron(II) using 2-thiophenaldehyde-4-phenyl-3-thiosemicarbazone as derivatizing reagent

The complexing reagent 2-thiophenaldehyde-4-phenyl-3-thiosemicarbazone (TAPT) was examined for high performance liquid chromatographic (HPLC) separations of cobalt(II), copper(II) and iron(II) or cobalt(II), nickel(II), iron(II), copper(II) and mercury(II) as metal chelates on a Microsorb C-18, 5-mum column (150x4.6 mm i.d.) (Rainin Instruments Woburn, MA, USA). The complexes were eluted isocratically with methanol:acetonitrile:water containing sodium acetate and tetrabutyl ammonium bromide (TBA). UV detection was at 254 nm. The solvent extraction procedure was developed for simultaneous determination of the metals, with detection limits within 0.5-2.5 mug ml(-1) in the final solution. The method was applied for the determination of copper, cobalt and iron in pharmaceutical preparation.     

New chromogens of the ferroin-type-I. Substituted triazines related to 6-cyano-2,2'-bipyridine

A spectrophotometric study has been made of the iron(II), cobalt(II), nickel(II) and copper(I) chelates of seven new compounds that contain the ferroin functional grouping. None of the new compounds proved to be superior to chromogenic reagents currently in use, but the results are of interest in designing new chromogens.     

Liquid chromatographic determination of chelates of cobalt (II), copper (II) and iron (II) with 2-thiophonaldehyde-4-phenyl-3-thiosemicarbazone

Summary A new chelating reagent 2-thiophenaldehyde-4-phenyl-3-thiosemicarbazone (TAPT) has been examined for high performance liquid chromatographic (HPLC) separations of cobalt (II), copper(II) and iron (II) or cobalt (II), nickel (II), iron (II), copper (II) and mercury (II) as metal chelates on a C₁₈, 5μm column (250×4 mm i.d.) The chelates were eluted isocratically with methanol: acetonitrile: water containing sodium acetate and tetrabutylammonium bromide (TBA), and detected at 254 nm. A solvent extraction procedure was developed for simultaneous determination of the metals with detection limits within 0.02–2.5 μ g.mL⁻¹. The method was applied to the determination of copper, cobalt and iron in natural waters.     

Determination of cobalt(II), copper(II) and iron(II) by ion chromatography with chemiluminescence detection

An optimized flow-injection manifold for the chemiluminescence determination of cobalt(II), copper(II), iron(II) and chromium(III) by their catalytic effect on the luminol reaction is described. Detection limits are 0.0006, 0.08, 0.3 and 0.1 ng ml^?1, respectively. The suppression effect of several carboxylic acids on the emission intensity is discussed. A procedure for the separation of cobalt(II), copper(II) and iron(II) on a low-capacity, silica-based cation-exchange column, using 5 mM oxalic acid at pH 4.2 as the mobile phase and post-column detection via the luminol reaction, is also described. Detection limits for cobalt(II) and copper(II) are 0.01 and 5 ng ml^?1, respectively.     

Synthesis of narrowly size-distributed metal salt/poly(HEMA) hybrid particles in inverse miniemulsion: versatility and mechanism

Hybrid particles containing different hydrophilic metal salts such as tetrafluoroborates of iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), and nitrates of cobalt(II), nickel(II), copper(II), zinc(II), and iron(III), and cobalt(II) chloride were synthesized via inverse miniemulsion polymerization of 2-hydroxyethyl methacrylate (HEMA). All salts delivered narrowly size-distributed hybrid particles with the exception of iron(III), where only the nitrate salt could be successfully employed. The size and size distribution of the hybrid particles were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The particle morphology and the distribution of salt in the dried particles were observed by TEM. The influences of the type of metal salts and salt content on the particle size distribution were extensively investigated.     

Chelating ion-exchangers containing n-substituted hydroxylamine functional groups: Part V. Iron,copper, and uranium separations on Duolite CS-346 resin

The separation of iron(III), copper(II) and uranyl(II) ions from a series of salt solutions by chelating ion exchange on Duolite CS-346 resin by pH control is described. Recoveries of these ions from cobalt and nickel salt solutions were quantitative. Iron may also be separated from copper by selective sorption with pH control, and uranium from iron and copper by selective desorption with sodium carbonate solution as eluent.     

Synthesis and characterization of iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of salicylidene-N-anilinoacetohydrazone (H2L1) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H2L2)

Salicylidene-N-anilinoacetohydrazone (H(2)L(1)) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H(2)L(2)) and their iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by IR, electronic spectra, molar conductivities, magnetic susceptibilities and ESR. Mononuclear complexes are formed with molar ratios of 1:1, 1:2 and 1:3 (M:L). The IR studies reveal various modes of chelation. The electronic absorption spectra and magnetic susceptibility measurements show that the iron(III), nickel(II) and cobalt(II) complexes of H(2)L(1) have octahedral geometry. While the cobalt(II) complexes of H(2)L(2) were separated as tetrahedral structure. The copper(II) complexes have square planar stereochemistry. The ESR parameters of the copper(II) complexes at room temperature were calculated. The g values for copper(II) complexes proved that the Cu-O and Cu-N bonds are of high covalency.