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The hydrolytic activity of ethriol phosphite and triphenyl phosphite in the p-xylene/water two-phase system was studied by the31P NMR method. It was shown that the rate of hydrolysis can be controlled by varying the pH of the aqueous phase. Hydrolysis of triphenyl phosphite is much slower than that of ethriol phosphite in the tested pH range. Coordination of ethriol phosphite with a rhodium carbonyl complex completely suppresses its hydrolysis.

The interaction of nickel and iron acetylacetonates with hydrolysis products of titanium and zirconium alcoholates and their mixture has been studied. It was shown that chemical synthesis of organometallic gels followed by heat treatment makes it possible to form complex single-phase binary or ternary oxides. For the first time single-phase metal-containing titanate, zirconate, and titanate-zirconate oxides have been produced and their structure and magnetic and local electronic properties characterized.

N-Alkylpiperidines with alkyl fragment length from C1 to Cl5 were synthesized by the reaction of CO + H2 + piperidine. The molecular mass distribution of the N-alkylpiperidines has two different distribution parameters α. Thus, α=0.45±0.03 for C1-C5 alkyl fragments, while α=0.65±0.02 for C6-C15. Piperidine was found to act as a modifier reagent and chemical trap for the intermediates in the synthesis reaction.

The factor responsible for the deactivation of a carbonyl triphenylphosphite rhodium hydroformylation catalyst appears to be the formation of a chelate-structure complex with diphenylphosphite, which is the product of partial hydrolysis of the organophosphorus ligand. The deactivating effect of diphenylphosphite can be suppressed upon interaction of the H(O)P(OPh)2 and P(OPh)3-modified complex with 2-butenes under hydroformylation reaction conditions.

In a study of the reaction of 2,2-dimethyl-1-propanol, 2-ethyl-1-hexanol, 2-octanol, and 4-heptanol or 4-heptanone and 2-octanone with aminating agents such as ammonia, dimethylamine, and propylamine in the presence of hydrogen on a fused iron catalyst, we showed that the desired amines are formed through both “imine” and “enamine” mechanisms.

A number of new heterogeneous phase transfer catalysts based on polymeric dibenzo-crown-ethers supported on the carbonaceous material “Sibunite”, ultrafine diamonds, or silica gel are synthesized. The activity of several of the catalysts for the reaction of 1-bromooctane with KI is higher than that of previously known analogs. The catalytic effect depends on the support, linker, and solvent.

The gas-phase heterogeneous catalytic reductive dimerization of benzaldehyde to trans-stilbene and dibenzyl was carried out on a reduced promoted fused iron catalyst. The mechanism of this reaction was examined.

Epimerization of borneols was noted upon their reaction with ammonia and/or hydrogen on a fused iron catalyst. Borneols are hydroaminated to give bornylamines with predominance of the endo isomer.

strated in our previous work [2]. The contribution of enamine species has remained unclear. In order to clarify the role of enamine species in the amination of alcohols, we studied the reaction of l-octanol, 2-octanol, and 4-heptanol by dimethylamine (DMA). The formation of the corresponding tertiary amines in this case is clearly possible only with the participation of enamine intermediates. The experimental method and composition of the fused iron catalyst were presented in our previous work [2]. The products obtained were analyzed by gas-liquid chromatography on a Chrom-5 chromatograph and identified by chromato-mass spectrometry on a Kratos MS25RF instrument. At 250-265~ and 2-3 MPa with H2:DMA:alcohol ratio in the range 20-30:4-6:1, these alcohols gave 87% N,N-dimethyl-(l-octylamine), 74% N,N-dimethyl-(2-octylamine), and 37% N,N-dimethyl-(4-heptylamine). Thus, amine formation on the iron catalyst may also proceed by the enamine mechanism

1. The number and activity of the oxidative centers in H-mordenite depend on the conditions of preliminary heat treatment. At low temperatures of heating (150–200°C) in the presence of O2, H-mordenite already acquires the ability to adsorb hydrocarbons with the formation of cation radicals. 2. Decationized mordenites with a degree of substitution of Na+ ions for H+ less than 50% are inactive in the formation of cation radicals. 3. On the basis of the data obtained and an analysis of the interatomic distances in the structure of mordenite, it was hypothesized that during the process of its heat treatment in the presence of O2, together with the centers including Al3+ ions, centers\(\begin{array}{*{20}c} \backslash \\ - \\ / \\ \end{array} Si - O^. \), active in the formation of cations radicals of benzene, arise.

1. The catalyst NiO-SiO2 acquires activity in the reaction of dimerization of C2H4 when Al2O3 is introduced into it. 2. With increasing Al2O3 content in the catalyst, the conversion of C2H4 and i-C4H8 and the number of electron acceptor centers, recordable by ESR, pass through a maximum (1–3% Al), while the total acidity of the catalyst increases.

It was found by the NMR method (1H and13C) that in the reaction of (1,2),(3,4),(5,6)-tripropanobenzene (Ia) and (1,2),(3,4),(5,6)-tributanobenzene with SHO2BF4 in “superacids,” complexes of the arene·NO+ type are formed.

1. The homogeneous stoichiometric reaction of synthesis of aromatic alcohols in the reaction of iron carbonyl complexes of phenylacetylene with CO and H2, the model of analogous heterogeneous synthesis on a melted iron catalyst, was conducted. 2. Complexes with a binuclear structure exhibit significantly higher reactivity than mononuclear complexes.

A chromatomass spectrometric method of studying C4-C10 aliphatic diols in complex mixtures using silylation directly in the chromatographic column with N,O-bis (trimethylsilyl) trifluoroacetamide was developed.

1. The activity of catalysts containing 2 and 20% NiO on SiO2-Al2O3 in dimerization reactions of ethylene depends on the Al2O3 content. 2. The degree of oligomerization of isobutylene and double-bond migration in n-butenes, formed by ethylene dimerization, changes in agreement with the total acidity of the catalyst on 2% NiO-SiO2-Al2O3 catalyst.

1. The method of photoelectron spectroscopy has been used to show that the Co and Mo ions of CoO-MoO3-Al2O3 catalysts interact with the γ-Al2O3 lattice, the Mo ions blocking the penetration of the Co ions. Formation of metallic Co promotes extensive Mo ion reduction. 2. Thermal treatment of the CoO-MoO3-Al2O3 catalyst in air tends to enrich the surface with respect to Mo ions, while reduction enriches the surface with respect to Co ions. 3. Oxidational treatment of the CoO-MoO3-Al2O3 and MoO3-Al2O3 catalysts is required for formation of anthracene radical-cations. A description is given of an oxidizing center structure which accounts for the reduction in acceptor activity of the Mo6+ ions in the ternary system.

1. The hetero-catalytic reaction of phenylacetylene, carbon monoxide, and hydrogen has been effected over a fused iron catalyst to form aromatic alcohols in which the phenylacetylene plays the part of initiator and reagent. 2. Additional experimental support has been obtained for the chain character of the catalytic synthesis of organic compounds from carbon monoxide and hydrogen.

1. The catalytic synthesis of α,ω-diols and their derivatives was carried out from CO, H2, and acetylenic alcohol or its ethers. 2. A study of the individual steps in the mechanism of the synthesis of bifunctional compounds from CO, H2, and substituted acetylenes showed that chain propagation proceeds as a result of the consecutive addition of CO and H2 to primary and intermediate complexes without their prior reaction with each other.

The introduction of an organosilicon fragment into the hydrocarbon chain connecting the phosphorus atoms in a diphosphine does not affect the properties of this compound as a modifier of cobalt carbonyl catalyst for olefin hydroformylation. The use of O-methyl-bis(dibutylphosphinoethyl)methylsilane as the modifier leads to the formation of an active and selective cobalt carbonyl catalyst for olefin hydroformylation.

Aliphatic alcohols are not aminated under Fischer-Tropsch synthesis conditions modified by amines or ammonia on an iron catalyst. Alkylamines are probably formed by the hydroamination of surface species.

1. Dissolution of (1,2),(3,4),(5,6)-tripropanobenzene in HSO3r-SbF5-SO2FCl generated the 1H-(1,2),(3,4),(5,6)-tripropanobenzenonium ion, which is converted by the action of Cl2 to the 1-chloro-(1,2),(3,4),(5,6)-tripropanobenzenonium cation, NMR spectroscopy indicates that these ions undergo a degenerate rearrangement by 1,2-shift of the H and Cl atoms, respectively, at approximately the same rate to C2 and C6. 2. The experimental value of ΔG≠ of the 1,2-chlorine shift in the chlorosubstituted cation is close to that expected on the basis for the reported dependence of ΔG≠Cl on δC+, while the ΔG≠ value for the unsubstituted ion is significantly lower than that expected. This is probably a consequence of a difference in the sensitivity of the σ- and n-type orbitals (H and Cl atoms, respectively) to the effect of orbital orientation.

1. Fine paramagnetic clasters of the ɛ-carbide, with a particle size of ∼30–50 A, are formed in the initial step of the carbidization of the promoted iron catalyst for the synthesis of organic compounds from CO and H2. 2. The clasters are apparently deposited in the vicinity of the flat or linear defects of the crystal. The high value of the quadrupole splitting (ΔEQ∼0.9 mm/sec) and the absence of magnetic ordering testify to the flat, lamellar nature of the particles. 3. The coarse magnetically ordered blocks of the bulky iron ɛ-carbide are formed via growth and aggregation (cross linking) of the lamellar colonies of fine particles.

When the amount of aluminum in a nickel-containing mordenite with variable degree of dealuminization is increased the total acidity of the zeolite increases, the concentration of the electron-acceptor centers, recorded by the EPR method, passes through a maximum, while the degree of ethylene conversion varies within narrow limits.

It was shown that butyne-1 and hexyne-1 (monosubstituted acetylenes) initiate the synthesis of alcohols from CO and H2 on fused iron catalysts. Acetonitrile, butynediol, propargyl halides, and diethylacetylene do not initiate the process.

1. In the decomposition of nickel tetracarbonyl that is adsorbed on the surface of activated x-ray amorphous lamellar silica, the silica structure undergoes crystallization. 2. When nickel is selectively removed from the surface of the silica matrix, the skeleton of the newly formed crystal structure does not change.

1. An increase of reactivity of iron and of its surface compounds occurs as the result of the activation or breaktng-in of fused iron catalysts, which had been reduced with hydrogen at 1000°, under the conditions of synthesis of hydrocarbons from CO and H2, this increased reactivity being shown in their reactions with CO, H2 and other reaction mixture components. 2. A hypothesis was advanced about the conjugated mechanism of the catalytic action of iron catalysts, according to which the synthesis from CO and H2 is induced by reactions of carbon monoxide and hydrogen with the iron and its compounds on the surface of a working catalyst.