V. K. Polovnyak

Complexing processes on the immobilized matrices of hexacyanoferrate(II)-nickel(II) and nitrogen-sulfur ligands in thin gelatin layer

SummaryComplexing processes occurring between immobilized matrices obtained from Ni(II) hexacyanoferrates(II) and solutions of various nitrogen-sulfur-containing chelating ligands in thin gelatin layers have been studied. With Ni2[Fe(CN)6]-matrix, the complexing process is found to proceed according to a SN2-mechanism. The schemes of the processes in each of the above matrices are given. Examples of kinetic curves for particular systems “hexacyanoferrate(II) nickel(II)-ligand” are presented.ZusammenfassungEs wurden Komplexierungsprozesse auf immobilisierten Matrices, die von Ni(II)-Hexacyanoferrat(II) und Lösungen verschiedener Stickstoff-Schwefel-Liganden erhalten wurden, in dünnen Gelatin-Schichten untersucht. Mit einer Ni2[Fe(CN)6]-Matrix wurde festgestellt, daß der Komplexierungsprozeß nach einem SN2-Mechanismus verläuft. Es werden die entsprechenden Reaktionsschemata angegeben. Beispiele für den kinetischen Verlauf für bestimmte „Hexacyanoferrat(II)-Ni(II)-Ligand“-Systeme werden präsentiert.

Kinetics of homogeneous dehydrogenation of formic acid in the presence of supramolecular rhodium(III) complex with P-functionalized calix[4]resorcine

The kinetics of homogeneous dehydrogenation of formic acid in the presence of supramolecular rhodium(III) complex with P-functionalized calix[4]resorcine were studied in dioxane, tetrahydrofuran, dimethylformamide, and binary formamide-dioxane mixtures (volume ratio 10: 90, 20: 80, 30: 70) over a wide temperature range (40–90°C). The examined Rh(III) complex catalyzed the dehydrogenation process, and its catalytic activity was higher than that observed previously for rhodium complexes with non-macrocyclic phosphorus-containing ligands. The dehydrogenation rate constants were proportional to neither catalyst concentration nor dielectric constant of the medium, which is likely to be related to supramolecular nature of the Rh(III) complex. No micelle formation was observed in the examined systems.

Reaction of rhodium trichloride with P-functionalized calix[4]resorcinols in various media

The features of the reaction of rhodium trichloride with calix[4]resorcinols modified with various types of phosphorus-containing groups in ethanol, ethanol-formate medium and acetone under an inert atmosphere were studied. Neutral complexes were isolated in the solid form, the solvent molecules were shown to be actively involved into the formation of the final reaction products. The compounds were characterized by IR, Raman, 31P NMR, ESR, X-ray photoelectron and electronic spectroscopy, and electric conductivity. The composition was confirmed by the data of elemental analysis, X-ray fluorescence analysis, and derivatography. Based on the analysis of the ESR spectrum, the electronic and geometric structures of the paramagnetic product isolated from the acetone medium was determined.

Complexes of dirhodium(II) carboxylates with calix[4]resorcinarenes functionalized at the upper and lower rim of the molecule with P,N-containing Fragments

AbstractThe features of the reaction between dirhodium(II) carboxylate and calix[4]resorcinarenes modified with various type functional groups at the upper and lower rim of the molecule in protic anhydrous solvent (ethanol) under inert atmosphere were investigated. Neutral complex compounds were isolated formed as a result of substitution of a water molecule by the macroligand in the axial position with respect to the R

Sorption Properties of Phosphorylated Indoles

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Complexes of Platinum(II) Chloride with Cyanophosphines

Rh bond occurring with the conservation of the latter. The compounds were characterized by 31P NMR, UV, IR, Raman, and ESR spectroscopy. Their composition was confirmed by elemental analysis.

Complex Formation of Potassium Hexachloroplatinate with 18-Crown-6 and Dibenzo-18-Crown-6 in Acetonitrile

Specific features of the reaction of anhydrous PtCl4 with 18-crown-6 in anhydrous solvents with different donor and solvating abilities, such as nitromethane, acetonitrile, and 1,2-dichloroethane, under an inert atmosphere are studied. Ionic platinum complexes with oligoethylene glycols or with crown ethers, formed by macroring opening and/or fragmentation under the action of the acidic agent, were isolated. The 1H NMR, IR, and Raman spectra of the complexes were studied. To assess the coordination mode of the crown ether cleavage product with Pt(IV), quantum-chemical calculations at the density functional theory level were carried out.

cis-[Chlorotriphenylarsinopalladium(I)-(μ-carbonylo)chlorotriphenylarsinopalladium(I)] as a new arsenic-containing catalyst

Sorption properties of 1- and 3-substituted indoles containing a P(III) atom were estimated by gas chromatography. The sorption properties were shown to depend on the nature of substituents on the phosphorus atom.