Silver chloride extraction from hydrochloric acid solutions with triisobutylphosphine sulfide (CYANEX 471, L) in the presence of organic proton-donor additives (HR) was studied. Both alkyl-, bromo-, nitro-substituted phenols, and organic acids of various structures were used as additives. A new synergistic effect (S) was found to take place in the presence of the additives. The degree of the synergistic effect in the systems containing phenols decreases in the series 4-nitrophenol > 4-bromophenol > 4-tert-butylphenol > 2,6-dimethylphenol > 2-methyl-6-cyclohexylphenol > 2,6-bis(tert-butyl) phenol. In the systems containing organic acids, the following series is observed: dinonylnaphthalenesulfonic acid (DNNSA) > 4-tert-butylphenol > caprylic acid > di(2-ethylhexyl)phosphoric acid > bis(2,4,4-trimethylpentyl)phosphinic acid. Based on the analysis of the extraction data and the IR and NMR spectra of the extracts, it was concluded that an increase in the silver extraction with CYANEX 471 in the presence of HR is due to the formation of the compound [AgCl center dot 2L center dot HR] in the organic phase. It was shown that a mixture of CYANEX 471 and 4-tert-butylphenol can be used for the highly selective extraction of silver from hydrochloric acid solutions containing metal impurities (Ni, Cu, Co, Zn, Fe(III), and Na). The mixtures of CYANEX 471 with alkylphenols or DNNSA, in which the high synergistic effects (S >= 10 and >= 50, respectively) take place, can efficiently be used for processing different industrial silver chloride solutions.

Abstract : The paper presents data on nickel, cobalt and zinc extraction from sulphate solutions with nonane-diluted bis(2,4,4-trimethylpentyl)dithiophosphinic acid (HR). An IR spectroscopy method is used to examine the state of HR in nonane, and it was shown to exist as a monomer up to a concentration of 0.1 M. With a further increase in concentration, the acid forms associated species. The value of the concentration of the monomeric form is determined as a function of the total HR concentration in nonane in the range of 0.0–1.0 M. Based on the comparative analysis of the extraction equilibrium data together with information from the visible and IR absorption spectra of the extract, the configuration of the nickel, cobalt and zinc complexes in the organic phase was determined.

A reaction of 2,3-xylenol, 2,3-dichlorophenol, and 1,3-disubstituted benzenes with 1-adamantanol in trifluoroacetic acid leads to the corresponding monoand diadamantylated products.

Abstract : The paper presents data on nickel, cobalt and zinc extraction from sulphate solutions with nonane-diluted bis(2,4,4-trimethylpentyl)dithiophosphinic acid (HR). An IR spectroscopy method is used to examine the state of HR in nonane, and it was shown to exist as a monomer up to a concentration of 0.1 M. With a further increase in concentration, the acid forms associated species. The value of the concentration of the monomeric form is determined as a function of the total HR concentration in nonane in the range of 0.0–1.0 M. Based on the comparative analysis of the extraction equilibrium data together with information from the visible and IR absorption spectra of the extract, the configuration of the nickel, cobalt and zinc complexes in the organic phase was determined.

A reaction of cis-diamminedichloroplatinum(II) with the natural polysaccharide arabinogalactan gave a product characterized by X-ray powder diffraction, IR spectroscopy, UV spectrophotometry, and thermogravimetry. It was demonstrated that cis-diamminedichloroplatinum(II) is bound to arabinogalactan by a linkage between its -C-O-C- bond and the hydrogen atom of the NH3 group of the starting complex. The product can suppress tumor growth with no toxic effect on the organism.

The electrochemical reactions of carbonyl cluster compounds M 3 (CO) 12 (M = Fe, Ru, Os) were compared with those of [Fe 5 C(CO) 14 ] 2− and [Fe 6 C(CO) 16 ] 2− in different aprotic solvents. The stability of electrochemically generated products of these clusters in the studied solvents was shown to grow in the following order: tetrahydrofuran < acetone < dichloromethane < acetonitrile.

Regularities of sorption extraction of platinum(II, IV) and rhodium(III) by anion exchangers of various physical and chemical structure in the presence of hydrochloric media were studied. It is established that AM-2B, Purolite A 500, and Purolite S 985 ionites adsorb complex anions of platinum metals employing mixed mechanism. A high affinity of the studied anionites for the studied complex anions of platinum and rhodium is established.

4-(1-Adamantyl)-, 5-(1-adamantyl)-, and 4,6-bis(1-adamantyl)pyrogallols were obtained by the reaction of adamantan-1-ol with pyrogallol in trifruoroacetic acid. The reaction of pyrogallol with adamantan-1-ol at 200 °C in a solvent-free medium without catalysts resulted in 5-(1-adamantyl)pyrogallol.

An IR-spectroscopy method is used to examine the state of nonane diluted bis(2,4,4-trimethylpentyl)dithiophosphinic acid (HR) in the presence of various electron-donor additives (L). Trioctyl amine (TOA), n-octanol, trioctylphosphine oxide (TOPO), tributylphosphate (TBP), and triisobutylphosphine sulfide (TIBPS) were used as additives. The formation of hydrogen bonded complexes (H-complexes) via proton transfer and a [TOAH+][R-] ion pair was shown to occur in the system containing HR and TOA. For the other additives, except n-octanol, during the formation of the H-complexes, hydrogen bonding without proton transfer takes place. In the HR and n-octanol mixture H-complexes having a structure in which the acid exhibits both proton and electron-donor properties are formed. The concentrations of the monomers (CHR) and the activity coefficients for the dithiophosphinic acid (HR(tot)) in the presence of the additives were calculated. It was shown that CHR and HR(tot) depend essentially on the type of additive and that their values decrease when passing from n-octanol to TOA. The strength of the interaction between HR and L decreases in the series TOA TOPO TBP TIBPS n-octanol. This series coincides with the basicity series of the additives. An antagonistic effect takes place when zinc is extracted with the HR and L mixture, where L is the trialkyl amine (TAA), the trialkyl phosphine oxide (TAPO), TBP, and n-octanol. A decrease in extraction is observed in the series TAA TAPO TBP n-octanol. This series coincides with the series for decreasing HR activity in the presence of additives. Thus a decrease in the extractant activity resulting from the interaction between HR and L is the determinant factor during zinc extraction with bis(2,4,4-trimethylpentyl)dithiophosphinic acid in the presence of the electron-donor additives.

An IR spectroscopy method is used to examine the state of nonane and toluene diluted bis(2,4,4‐trimethylpentyl)dithiophosphinic acid (HR) in the concentration range of 0.025–1.0 M. It was found that in contrast to the “inert” solvent nonane, in which marked self‐association of the dithiophosphinic acid due to the formation of intermolecular SH…S hydrogen bonds begins at an HR concentration of ∼0.1 M, in the aromatic diluent toluene this process begins at HRtotal ⩾0.4 M. This result is explained by the interaction of the proton of the S‐H group of the dithiophosphinic acid with the π‐electron system of the toluene aromatic ring and the formation of SH…π hydrogen bonds, preventing the self‐association of the organic acid. The presence of the monomeric, dimeric, and tetrameric forms of the extractant in solution was shown to best describe the bis(2,4,4‐trimethylpentyl)dithiophosphinic acid‐nonane system. The formation constants of the dimers (K2 = 0.78 ± 0.07) and tetramers (K4 = 3.42 ± 0.26) have been calculated.

The reactions of Cp(CO) 2 Re=C=CHPh ( 2 ) with M(PPh 3 ) 4 (M = Pd, Pt) gave the μ-vinylidene complexes Cp(CO) 2 RePd(μ-C=CHPh)(PPh 3 ) 2 ( 3 ) and Cp(CO) 2 RePt(μ-C=CHPh)(PPh 3 ) 2 ( 1 ), respectively. The substitution of Ph 2 PCH 2 PPh 2 (dppm) for the PPh 3 ligands in 1 resulted in the formation of Cp(CO)RePt(μ-C(1)=C(2)HPh)(μ-CO)(dppm) ( 4 ). The structure of complex 4 has been determined by single-crystal X-ray diffraction analysis. The structural and spectroscopic characteristics of complexes 1, 3 , and 4 were compared with the corresponding parameters of the manganese-containing analogs Cp(CO) 2 MnPd(μ-C=CHPh)(PPh 3 ) 2 ( 5 ), Cp(CO) 2 MnPt(μ-C=CHPh)(PPh 3 ) 2 ( 6 ) and Cp(CO) 2 MnPt(μ-C=CHPh)(dppm) ( 7 ).

Dihydric phenols and their monomethyl ethers were converted into diadamantyl derivatives by the reaction with 1-adamantanol in trifluoroacetic acid.

The paper presents data on nickel(II) extraction from sulphate solutions with nonane‐diluted bis(2,4,4‐trimethylpentyl)dithiophosphinic acid (HR). An IR spectroscopy method is used to examine the state of HR in nonane, and it was shown to exist as a monomer up to a concentration of 0.1 M. With a further increase in concentration, the acid forms associated species. The value of the concentration of the monomeric form is determined as a function of the total HR concentration in nonane in the range of 0.0–1.0 M. Based on the comparative analysis of the extraction equilibrium data together with information from the visible and IR absorption spectra of the nickel extract, the configuration of the nickel(II) complex in the organic phase was determined to be a low‐spin, square‐planar complex. The complex composition was found to correspond to the formula NiR2. The complex is hydrated, with the water very likely being bonded in the outer coordination sphere.

Liquid products of the autoclave hydrogenation and hydropyrolysis of the Barzas sapromixite were studied. Chromatomass spectrometry was used to determine the content of individual substances in the low boiling fractions. Hydropyrolysis product appeares to consist of normal paraffins by more than 50 mass %. Hydrogenation products is characterized by a higher content of cyclic and structure isomerized paraffins. Aromatics content in both products does not exceed 14.1 mass %. IR and NMR spectroscopy show that fractions boiling above 180 degrees C contain mostly aliphatic fragments. Hydropyrolysis products composition is similar to that of oil, while hydrogenation product is characterized by more aromatic and shorter aliphatic fragments per statistically average molecule. If mechanically activated iron ore catalyst is used at the sapromixite hydrogenation and hydropyrolysis, the contribution of distillate fractions increases, and low boiling (boiling start 180 degrees C) fractions contain more low molecular mass hydrocarbons.

The electrochemical behavior of the heteronuclear dimeric vinylidene complex [Cp(CO) 2 MnCu(μ-C=CHPh)(μ-Cl)] 2 (I) is studied using polarography, cyclic voltammetry, and controlled-potential electrolysis on mercury and platinum electrodes in acetonitrile. The dimer is reduced in two two-electron stages: at the first stage, metal-halogen bonds are broken and binuclear monomers [Cp(CO) 2 MnCu(μ-C=CHPh)(Cl)] − are formed; at the second stage, mononuclear manganese complexes Cp(CO) 2 Mn=C=CHPh, metallic copper, and chloride ions are formed. The two-electron oxidation of dimer [Cp(CO) 2 MnCu(μ-C=CHPh)(μ-Cl)] 2 also results in the formation of binuclear monomers, which decompose to complex Cp(CO) 2 Mn=C=CHPh, Cu 2+ ions, and Cl − ions.