V. I. Spitsyn

Oxidation-reduction properties of platinum complexes of the amino type

1. The oxidation-reduction potentials of a number of systems of the amino complexes of platinum were measured. It was shown that the systems containing the dihydroxo complexes of Pt(IV) are irreversible. 2. The dependence of the potentials of systems containing the dihalo complexes of Pt(IV) on the temperature in the range 10–50° was investigated; a study was made of the effect of the stability of the complex and the nature of the coordinated groups on the value of the potential; a thermodynamic characterization of the processes was given.

Crystal structures of cerium molybdenum and uranium molybdenum heteropoly acids

Conclusions1.Crystal structures of the cerium molybdenum and uranium molybdenum heteropoly acids have been determined for the first time.2.A short distance between oxygen atoms of two neighboring polyanions has been found, which allows the suggestion of the presence of a hydrogen bond between them.3.Distribution of the water molecules in the crystals of the acids is statistical.

Radiation centers in alkaline-earth hydroxides

Conclusions1.In polycrystalline specimens of magnesium and calcium hydroxides γ-irradiated at 77°K O− ion-radicals, surface Fs centers, and stabilized hydrogen atoms have been observed.2.Based on a study of the accumulation kinetics of the radiation defects it can be concluded that alkaline-earth hydroxides are unstable toward radiation.

Influence of cyclization of N,N′-ethylenediaminedisuccinic acid on its complex-forming properties

Conclusions1.A study has been made of the conditions for the occurrence of strucutral rearrangement when an aqueous solution of N,N′-ethylenediaminedisuccinic acid is heated in acid; this chelating agent, like other analogs of ethylenediaminediacetic acid, undergoes intramolecular cyclization, with a substantial decrease in its complex-forming properties.2.The hypothesis advanced in the literature that the chelating agent is decarboxvlated is not in accord with the facts.

Atomic hydrogen in γ-irradiated hydroxides of alkaline-earth elements

Conclusions1.We have detected for the first time stabilization of atomic hydrogen inγ-irradiated polycrystalline alkaline-earth element hydroxides.2.Depending on the degree of dehydroxylation, several types of hydrogen atoms may be stabilized in the hydroxides, these hydrogen atoms having different radiospectroscopic parameters.3.In the magnesium-calcium-strontium-barium hydroxide series, a regular decrease has been found in the hfi constants for H atoms with the cations in the immediate surroundings. A direct proportionality has been found between the parameters ΔA/A0 and the polarizability of the cation.

Structure of the basic uranyl salts and polyuranates

Conclusions1.The crystal structure of lithium triuranate Li2U3O10 has been determined. In the three-dimensional U3O10 framework two basic structural elements have been isolated: infinite chains of (UO2)O4 octahedra and infinite strips of (UO2)O5 pentagonal bipyramids. The similarity and difference between this structure and the structures of H2U3O10 and D2U3O10 are discussed.2.The crystal structure of Zn(UO2)2SO4(OH)4·1.5H2O — the first representative of uranyl hydroxosulfates — has been determined. In this structure there are hydroxouranylsulfate layers linked by bivalent cations. The hydroxo groups coordinated by UO22+ groups make the maximum use of their coordination possibilities, being tridentate-bridging ligands.

Electron-spin-resonance spectra of irradiated frozen aqueous solutions

1. It was found by the methods of ESE and optical spectroscopy that Cd (I) and Hg(I) ions, arising in the γ irradiation of aqueous solutions of salts of Cd(II) and Hg(II) at 77°K, are characterized by several types of sites of stabilization. 2. The formation of dimer ions Cd 2 3+ and Hg 2 3+ in the process of heating of aqueous solutions of salts of Cd (II) and Hg(II) at 77°K, as a result of generalization of one electron on the σ-bond, was demonstrated.

Complexation of ferric ions with glucosamine

ConclusionMathematical modelling was used to show the formation of mono and dihydro complexes with glucosamine and the H2Gl2+ form in physiological solution. The formation constants of these species were calculated.

Behavior of rare-earth dipivaloylmethanates and acetylacetonates under gas chromatography conditions

Summary1.Undesirable sorption of REM dipivaloylmethanates by the packing of a GC column decreases along the series La-Lu. Other conditions being equal, sorption of dipivaloyl-methanates is lower than that of the corresponding acetylacetonates.2.A β-diketonate is sorbed chiefly by the liquid phase, and in the form of a bis-β-diketonate cation with the separation of an equivalent amount of free protonated ligand.

Existence of hexachlorocerates(IV) of alkali metals

Conclusions1.X-ray diffraction analysts and low-temperature DTA have confirmed the formation of the unstable rubidium hexachlorocerate(IV) which is easily hydrolyzed with the formation of Ce(III) derivatives.2.It has been established that the Rb and Cs hexachlorocerates are isomorphous.3.The preparation of the hexachlorocerates(IV) of Li, Na, and K was unsuccessful (according to the low-temperature data).