Four new µ-oxamido heterobinuclear complexes have been synthesized and characterized, namely [Cu(oxpn)Fe(L)₂]SO₄, where oxpn denotes the N,N'-bis(3-aminopropyl)oxamidodianion and L represents 1,10-phenanthroline(phen);5-nitro-1,10-phe- nanthroline (NO₂-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 2,2'-bipyridine (bpy). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(II) and an iron(II) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. The [Cu(oxpn)Fe(bpy)₂]SO₄ (1) and [Cu(oxpn)Fe(phen)₂]SO₄ (2) complexes have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(II) ion, H = -2J S ₁S₂-D S_z², giving the exchange integrals J = -21.8 cm^-1 for (1) and J = -23.2 cm^-1 for (2). These results are commensurate with antiferromagnetic interactions between adjacent metal ions within each molecule.

Au(I) complexes of the type RCOOAuL, where R = C₆F₁₃, C₇F₁₅, C₈F₁₇, C₉F₁₉, C₆F₅, OOC(C₃F₆) and L - trimethylphosphine (Me₃P) were synthesized and characterized by spectroscopic (IR, ¹³C, ¹⁹F, ³¹P NMR) and thermal methods. Spectroscopic results favour two coordinated Au(I) with unidentate bonded trimethylphosphine and carboxylates, whereas in the case of hexafluoroglutarate a dimeric structure has been found. The mode of carboxylates binding was proposed basing on the chemical shift of COO group in ¹³C NMR spectra and splitting of COO asymmetric and symmetric vibrations bands. Thermal decomposition proceeds in a multistage way that results in metallic gold. Decomposition temperatures and thermal stability of the studied complexes depend on the length of the perfluorinated chain.

Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) succinates were prepared as solids with general formula MC₄H₄O₄^.nH₂O, where n = 3 for M = Ni, Co, n = 2 for M = Cd and n = 0 for M = Cu, Zn. IR spectra and X-ray diffractograms were recorded and solubilities in water and thermal decomposition in static air were investigated. During heating the hydrated complexes of Co(II)), Ni(II) and Cd(II) lose all water molecules in one step. All anhydrous complexes decompose to oxides MO with intermediate formation of free metals (Ni, Co, Cu) or oxocarbonates (Zn, Cd).

EI spectra of acetylacetone, alkali acetylacetonates and acetylacetonates of alkaline earths of formulae M(I)(acac) and M(II)(acac)₂ (where M(I) = Li, Na, K, Rb, Cs, M(II) = Be, Mg, Ca, Sr, acac = acetylacetonate ligand) were obtained using mass spectrometry. Ligand-ions were observed in each spectrum. Metal cations were present only for the elements of group I. The detection of polymeric species of general formula [M_x(acac)_y]⁺ supports the conclusion, that polymeric species of acetylacetonates of group I and II are commonly present in the gas phase.

The interactions between components in Zr-Cu-In ternary system at 870 K have been studied by X-ray and microstructure analyses. One earlier known (ZrCu₂In with MnCu₂Al-type) and four unknown ternary compounds have been found. Crystal structure of all new compounds are determined: ZrCu_5-xIn_x (x = 0.3-1.3) - AuBe₅ type of structure (space group F43m, a = 6.955-7.042(2) ); ZrCu_xIn_3-x (x = 0.35-0.80) - AuCu₃ type of structure (space group Pm 3m), a = 4.3281-4.3079(1) ); Zr₂Cu₂In - Mo₂FeB₂ type of structure (space group P4/mbm), a = 7.194(2) , c = 3.410(4) ; Zr₅CuIn₃ - Hf₅CuSn₃ structure type (space group P6₃/mcm, a = 8.671(2) , c = 5.917(1) ).

Complex of palladium(II) with 2-mercapto-1-methylimidazole has been prepared and studied by elemental analyses, X-ray diffraction, IR and far-IR spectroscopy and magnetic measurements. The crystal structure of the complex has been determined as follows: triclinic system, space group P1, a = 8.78(7) , b = 8.85(2) , c = 9.80(5) , = 66.7(5)^o, ß = 86.9(5)^o, = 72.0(1)^o, V = 664.3 ³.

A new series of Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes obtained by the template reaction of diacetyloxime and 1,2-diaminopropane with metal ions have been synthesized and characterized by elemental analyses, IR, VIS-UV, electrical conductivity, magnetic moment and ESR measurements. ESR spectrum of Cu(II) complex exhibits an axial type symmetry d_x²-y² with a covalent bond character. ESR spectrum of Ni(I) at 77 K formed by exposing the Ni(II) complex to ionizing radiation, points on d_x²-y² ground state. ESR spectrum of Fe(III) complex presents a low spin ⁵⁷Fe(I = 1/2), d⁵, configuration with d_z² ground state.

The ¹⁵N, ¹³C and ¹H NMR chemical shifts were measured for methylamine in the gaseous and liquid phase. The gas to liquid shifts reveal the deshielding effects for all investigated nuclei. It is shown that the hydrogen bonding is responsible for the largest changes, which are observed for the nitrogen and amino hydrogen atoms as well. The CHF-GIAO calculations indicate that the cyclic trimer of methylamine exhibits the shielding changes, which are in qualitative agreement with the gas to liquid shifts.

Six new 2-substituted-2-oxo-1,3,6,2-dioxaselenaphosphocanes were synthesized from bis(2-hydroethyl)selenide and alkyl or aryl phosphorodichloridates or phenylphosphonic dichloride.

Acyl iodides and bromides give in reaction with ylides 1 the expected 4-C- or O-acylation products 2 or 3. In contrast to acyl iodides and bromides, acyl chlorides give in reaction with the ylides 1 Wittig-like reaction products 4 (4-(1-chloroalkylidene)-5(4H)-oxazolones), whereas benzoyl fluoride gives 4-(1-benzoyloxybenzylidene)-5(4H)-oxazolones. Some evidence points to a mechanism of the formation of Wittig-like reaction products involving O-acylated ylides as intermediates.

Two C-peptides corresponding to sequences of genetic variants of bovine proinsulin have been synthesized by solid-phase method. C-peptide containing material has been isolated from two bovine pancreata using acid-ethanol extraction, gel filtration on Sephadex G-50 and ion exchange chromatography on carboxymethyl cellulose. Comparison of these materials with synthetic standards on reverse-phase HPLC have revealed that both pancreata contained only one variant of C-peptide which had Pro in position 16. The second variant of bovine proinsulin C-peptide with Leu at this position has not been detected. The corresponding genetic variant of bovine proinsulin, containing Leu within C-peptide sequence, has been found by other authors in the material obtained from a pool of a large number of pancreata. Our results exclude the possibility that the two bovine proinsulins are a result of expression of two insulin genes in the bovine species as a whole. The same C-peptide was found in ovine and bisontine pancreata.

The electron ionization-induced fragmentation patterns of cis-3a,4,9,9a-tetrahydro-4-methyl-2-phenyl-1H-pyrrolo[3,4-b]quinoline-1,3(2H)-dione derivatives have been studied. It was found that fragmentation starts at the N-phenylsuccinimide ring and its pattern depends on the type and position of the substituents at carbon atoms 5-8. Peaks, which can be assigned to the products of the retro Diels-Alder opening of the nitrogen atom containing tetrahydroquinoline ring, were observed.

A series of racemic methyl phosphinylacetates was hydrolyzed in the presence of porcine liver esterase (PLE) under the kinetic resolution conditions to give the corresponding P-chiral phosphinylacetic acids and recovered esters in high enantiomeric purity (72-100% ee). The Jones' active site model was applied to explain the enantioselectivity of this reaction.

Oxidation of pyridoxal (PL) by Cr₂O₇^2- ion has been studied using an excess of the aldehyde under air or argon atmospheres. The reaction leads mainly to two Cr(III) complexes: [Cr(PA)(H₂O)₄]²⁺ and [Cr(H₂O)₆]³⁺ and to uncoordinated pyridoxic acid (PA). The rate of PL oxidation follows a mixed third order rate law: first order in concentrations of Cr(VI), PL and H₃O⁺. The reduction of Cr(VI) to Cr(III) proceeds through chromium(V) intermediate complex, which has been detected by the EPR method. Mechanism of the reaction has been discussed.

The kinetics of oxidation of the mixture of S-phenylmercaptoacetic acid (PMA) and oxalic acid with pyridinium chlorochromate (PCC) in 30% (v/v) acetic acid-water exhibits a first-order dependence each in [PCC] and [PMA], at low concentrations of the latter. At high concentration of the substrate, a fractional order in [PMA] is observed. The rate increases linearly with [oxalic acid]. Increased reactivity in the presence of oxalic acid with carbon dioxide as one of the products is well explained by Rocek's mechanism for cooxidation, involving a ternary complex. Formation of a ternary complex at low concentrations and decomposition of the complex at higher concentrat-
ions of PMA is considered to be the respective rate-limiting step.

Basicities of p-toluidine, m-toluidine, p-chloroaniline, m-chloroaniline and m-nitroaniline N-glucopyranosylamines have been determined by potentiometric titration in methanol at 25^oC. The pK_b values of successive N-glucosides have been derived from the Broensted relation, log k = f (pK_b), using the rate constants of mutarotation, k. The same relationship served for the determination of basicities of several substituted anilines in methanol at 25^oC. Basicity constants of the aniline derivatives and of the N-arylglucopyranosylamines in methanol have also been correlated with analogous constants of the compounds in water.

Anation of cis-[Cr(bpy)₂(H<->₂O)₂]³⁺ ion (bpy = 2,2'-bipyridine ) in HN₃/N₃^- media gives a novel very inert monoazidocomplex whose formula and structure can be proposed as cis-[Cr(N₃)(bpy)₂(H₂O)]²⁺. This complex decomposes rapidly by addition of Cr_(aq)²⁺ into a deareated acidic solution. Analysis of the reaction products and the kinetics suggests an electron transfer Cr(II) -> Cr(III) via competitive reaction pathways: inner-sphere through Cr(III)-N₃-Cr(II) intermediate, outer-sphere and/or perhaps also via a more direct interaction of Cr(II) with p-ring of the coordinated bipyridine.

Carbonaceous materials were promoted by consecutive impregnation with manganese salt (potassium permanganate with or without the addition of sulphuric acid) and iron salt. Texture of the materials obtained was studied by low temperature argon sorption and manganese and iron distribution by X-ray photoelectron spectroscopy. The influence of impregnating solution on the structure of the catalysts studied was discussed. Catalytic properties (activity and selectivity) in selective catalytic reduction of nitric oxide with ammonia of doubly promoted carbonaceous material were compared with iron or manganese-containing active carbon.

The main purpose of this study was to investigate the segregation and oxidation of phosphorus on the polycrystalline iron surface using the AES and XPS methods. The segregation of phosphorus begins at 600 K and the maximum concentration of phosphorus on the surface is achieved at 720 K, as in the case of a monocrystalline sample. The segregation of sulphur begins above 720 K, whereas the phosphorus surface concentration decreases. The oxidation of the iron surface covered with phosphorus results in the formation of both the oxygen-phosphorus bonds and the oxygen-iron bonds. The different forms of surface species have been proposed.

Equilibrium isotope effect in the exchange reaction of deuterium between phenol (P), 2-isopropylphenol (IPP), 2,6-diisopropylphenol (DIPP), 2,6-ditertbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied at 298 K. The fractionation factors () have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulphoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that ln correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore it was found that in DTBT-TBT-base system ln depends linearly on the basicity of the solvent (DN parameters). On the other hand, ln correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition

Trisaquo(µ-pyrazine-2,3-dicarboxylato)strontium(II), SrC₆H₈N₂O₇ crystals have been studied by X-ray diffraction. The strontium ion is coordinated by a heteroring nitrogen, Sr-N of 2.793 , and one oxygen atom belonging to a monodentate carboxylic group, Sr-O of 2.583 , situated close to this nitrogen atom. Two oxygen atoms of carboxylic groups belonging to adjacent complex molecules, Sr-O = 2.647 and 2.914 , bridge them into ribbons. Each oxygen atom of the above group is also linked to the Sr ions belonging to adjacent ribbons, Sr-O = 2.576 and 2.620 , forming molecular sheets, which are parallel to the (010) plane. Each Sr ion coordinates also three oxygen atoms of water molecules (the average distance is 2.669 . Hydrogen bonds of 2.66(1)-2.84 (1) link the sheets into a 3-dimensional framework.

A new rhenium nitrosyl complex has been synthesized and characterized by IR, UV-Vis, NMR (¹H and ³¹P) and magnetochemical measurements. The crystal and molecular structure of [ReBr₃(NO)(MeCN)(PPh₃)] has been determined by X-rays. The Re atom is of six-coordinate distorted octahedral configuration and linear nitrosyl ligand is trans towards the acetonitrile molecule.