The dependence of the air-release time on the composition of flame‑retardant oil derived from mixed phosphate esters made using phenol and 4‑tert‑butylphenol (tert‑butylated oil) was studied. The air-release time is a function of the ratio of the major components, namely, (tert‑butylphenyl) diphenyl phosphate (II) and di(tert‑butylphenyl) phenyl phosphate (III), and rises sharply with an increasing content of tri(tert‑butylphenyl) phosphate (IV); triphenyl phosphate (I) has only a minimal effect. Esters II‑IV were isolated as pure compounds and characterized. The oil components, which are solids at room temperature, can form mixtures with pour point at –17°C and below. An empirical model was proposed for quantitatively describing the air-release time on the composition selected for tert‑butylated oils with physicochemical characteristics suitable for use in industry as fire‑resistant oils.

R-Oxo hydroformylation processes on rhodium phosphite complexes developed at LLC «RN-RD CENTER» are described – selective production of n-butyral from propylene (R-Oxo I), production of a mixture of n-butyral and isobutyral in equal parts (R-Oxo II), selective production of n-pentanal from a mixture of linear butenes (R-Oxo III). A scheme for the hydroformylation of propylene with membrane separation of the catalyst from the heavy reaction products is described.The analysis of the direction of using C3–C5 oxosynthesis products as raw materials for the production of ester lubricants is carried out.

The data review of low molecular olefin C2-C4 hydroformylation as a key step of oxygenate compound oxosynthesis is presented. The industrial and perspective cobalt and rhodium organometallic catalytic systems modified with phosphine and phosphite ligands as well as the industrial technological schema of hydroformylation assisted with such a catalysts are demonstrated.

A review of scientific and patent data on the hydroformylation of lower C2–C4 olefins in the oxo synthesis of oxygen-containing products is presented. Industrial and prospective catalytic systems based on organometallic compounds of cobalt and rhodium modified with phosphine and phosphite ligands and also industrial technological schemes involving such catalytic systems are examined.

A method is proposed for the regeneration of fire-resistant triaryl phosphate oils by heat treatment with anhydrous neutralizing agents with subsequent distillation of the reaction mixture. This treatment leads to the elimination of aging products in used triaryl phosphate oils such as acids, phenols, condensation products, wear metals, introduced sludge, and water. This method gives high yields of the regenerated oils meeting the standard requirements of fire-resistant triaryl phosphate oils for reuse.

According to the data of 1 H NMR spectroscopy, trimethylolpropane, di(trimethylolpropane), linear formals, and structures including a fragment of a cyclic formal are the main components of the bottom residue after vacuum distillation of raw trimethylolpropane yielded in the technological process of n -butyral condensation with formaldehyde proceeding by the Cannizzaro–Tishchenko reaction. The content of other impurities is minor. The heavy bottoms can be converted in high yield to a mixture of esters of trimethylolpropane and di(trimethylolpropane) by esterification with n -pentanoic acid. Such esters are characterized by a low pour point, high chemical resistance, thermal stability, and good viscosity-temperature properties, as well as sufficient compatibility with various plastic materials, and therefore, can be employed as lubricants, polymer plasticizers, and other products.

The method for the regeneration of used fire-resistant oils based on treating oils with an anhydrous neutralizing agent at heating, followed by rectification has been developed. As a result of such treatment, used triaryl phosphate oils are purified from a complex of aging products (acids, phenols, sealing products, wear metals, introduced sludge, water). The method provides high yieldsof regenerated oils with quality that meets the regulatory requirements for fire-resistant triaryl phosphate oils for reuse.

The physicochemical properties and production of fire-resistant oils derived from triaryl phosphates are discussed. The method for obtaining butylated oil developed at the Rosneft United Research and Development Center is described. The application of this method for resuming the production of fire-resistant oils and hydraulic fluids using raw materials available in the Russian Federation is examined.

The possibility of controlling the composition of a mixture of triphenyl phosphate, p-tert-butylphenyl diphenyl phosphate, di(p-tert-butylphenyl)phenyl phosphate, and tri(p-tert-butylphenyl) phosphate, formed by transesterification of triphenyl phosphate withp-tert-butylphenol, was demonstrated. The amount ofp-tert-butylphenol necessary for transesterification of triphenyl phosphate to yield a mixture of phosphates of required composition was determined. If necessary, the composition of the phosphates can be adjusted by selective distillation of triphenyl phosphate in a vacuum.

In this review, published information on the nature and molecular compositions of organochlorine compounds (OCCs), which are found in crude oil and in its refined products, is systematized. The native and added OCCs are reviewed. The formers are concentrated predominantly in high molecular weight resinous-asphaltene substances of crude oil, the latter’s, referred to as light organochlorine compounds, are present in the gasoline fractions. The following chemicals that are used for oil production are regarded as possible sources of OCCs: inhibited hydrochloric acid, acid compounds; organic solvents of asphalt-resin-paraffin deposits, organic solvents served for oil production stimulation, and possible products of a mutual solvent chlorination with hydrochloric acid.

A homogeneous catalytic system containing palladium( ii ) halides, diphenyl- m -sulfo-phenylphosphine (or palladium halide complexes with diphenyl- m -sulfophenylphosphine) and hydrohalic acid was developed and studied in the liquid-phase water gas shift reaction. The system based on palladium bromide and hydrobromic acid in aqueous acetic acid (20–40 vol.%) showed the highest activity. The dependences of the initial reaction rate on the concentrations of reagents and catalyst components were studied, a mechanism for the process was proposed, and a kinetic model was developed and found to agree well with experimental results.

Alcohols were obtained by the one-stage hydroformylation of olefins from the hydrocarbon fraction C 6 –C 9 , which was produced in the Fischer—Tropsch synthesis followed by the hydrogenation of aldehydes yielded by the hydroformylation products. The process is carried out on the cobalt catalyst modified by tertiary phosphines under the synthesis gas pressure 85 bar and temperature 180 °C. The role of the solvent is performed by paraffins of the hydrocarbon fraction from the Fischer—Tropsch synthesis. Cobalt acetylacetonate Co(acac) 2 , acetate Co(OAc) 2 , and carbonate CoCO 3 can serve as catalyst precursors. The complexes with bulky and basic phosphines were shown to possess satisfactory activity and high selectivity to alcohols. Tricyclohexyl- and triphenylphosphines are the most promising for the implementation of the process. The full conversion is achieved within 8 h at the cobalt concentration ∼0.2 wt.%: the residual olefin content is <1% and the selectivity to alcohols is ⩾97%.

The kinetics of propene hydroformylation in the presence of the catalytic system Rh(acac)(CO) 2 / n L (L = 2,2′-bis[(1,1′-diphenyl-2,2′-diyl)phosphito]-3,3′,5,5′-tetra- tert -butyl-1,1′-diphenyl, 0.5 < n < 20) in para -xylene at 90°C is reported. At n ≥ 2, the rate and regioselectivity of the process are independent of the L concentration. The reaction is of positive fractional order with respect to propene and hydrogen and of negative order with respect to CO. The molar ratio between the linear product and the branched product decreases with an increasing CO pressure and increases with an increasing H 2 pressure. The kinetic data are consistent with a process mechanism involving irreversible propene addition to the unsaturated hydride complex HRh(CO)L with the formation of the π-complex HRh(CO)L(C 3 H 6 ). The insertion of coordinated propene into the H-Rh bond of this complex is reversible in the linear aldehyde formation route and is quasi-equilibrium in the branched isomer formation route. The conclusions as to the character of these reaction steps are corroborated by the compositions of the but-1-ene and but-2-ene hydro-formylation products.

Numerous published data on the structure and thermodynamics of formation of molecular complexes are analyzed. The enthalpies of complexation (−ΔH) are related to the characteristic parameter Δr = [r DA−a 1(r D+r A)], where r DA is the donor-acceptor bond length determined by microwave spectroscopy and X-ray analysis, r D and r A are the tabulated values of the homopolar covalent radii of the heteroatoms that form the donor-acceptor bond, and a 1 is an empirical coefficient equal to 0.901±0.007. The relation between −ΔH and Δr values has the form −ΔH = a 2/Δr (a 2 = 21.6±1.6 kJ Å mol−1), with a mean relative error of approximation of about 15% and a correlation coefficient of 0.97. As the strength of the complex increases, the donor-acceptor bond length approaches the sum of the heteropolar covalent radii of the atoms involved in the bond (Δr tends to zero). At Δr ≫ 1, the strength of complexes is determined by weak van der Waals interactions between the complex components and the −ΔH values tend to zero.

Nanostructured nickel films deposited by laser electrodispersion onto a silicon (semiconducting) or thermally oxidized silicon (insulating) substrate show a remarkably high catalytic activity (of the order of 103–104 (mol product) (mol Ni)−1 h−1) in the isomerization of chlorinated hydrocarbons and olefin hydrogenation. The special properties of the laser-deposited films are likely due to the small size (2.5 nm), developed surface, and amorphism of the nickel particles, as well as to highly active, charged particles appearing on the insulating substrate. The latter result from thermal fluctuations of electrons between closely spaced particles. In a film deposited on silicon covered with a natural oxide layer, a significant role is also played by charge redistribution between the substrate and metal particles.

The kinetics of the catalytic reaction of styrene with CO and n -butanol in the Pd(dba) 2 —TsOH—Ph 3 P system in dioxane (383 Ê) was studied. The initial rates of accumulation of regioisomeric products (butyl 2- and 3-phenylpropionates) were measured as functions of the CO pressure, reactant concentrations, and the catalytic system components. A kinetic model of the process and a hydride mechanism with the HPd(Ph 3 P) 3 + cationic complex acting as a key intermediate were proposed.

Palladium clusters Pd 4 (SEt) 4 (OAc) 4 ( I ) and Pd 6 (SEt) 12 ( II ) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I , a = 9.774(2) Å, b = 10.821(2) Å, c = 13.061(3) Å, β = 92.88(3)°, V = 1379.6(5) Å 3 , ρ(calcd.) = 2.182 g/cm 3 , space group P 2 1 / n , Z = 4, N ref = 1558, and R = 0.031; for II , a = 10.581(1) Å, b = 10.584(2) Å, c = 11.478(2) Å, α = 101.62(1)°, β = 104.95(1)°, γ = 106.74(1)°, V = 1135.2(4) Å 3 , ρ(calcd) = 2.007 g/cm 3 , space group P 1, Z = 1, N ref = 2828, and R = 0.022. In cluster I , four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II , Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.

The reaction of phenylacetylene with CO and n -butanol in toluene (363 K) catalyzed by the Pd(dba) 2 / m (CF 3 COOH)/ n (Ph 3 P) system (dba is dibenzylideneacetone; 2 ≤ m ≤ 8; 10 ≤ n ≤ 30) is studied. The initial rate of the main product (butyl 2-phenylpropenoate) buildup is found to depend on the pressure of CO and the concentrations of reactants and system components. The state of the catalyst under reaction conditions is studied in situ by IR spectroscopy. A kinetic model is developed based on the experimental results. This model corresponds to the mechanism that resembles the hydride mechanism in the type of main intermediates in the catalytic cycle.

The single-factor experiment method was used to study the kinetics of styrene hydrobutoxycarbonylation catalyzed by the complex PdG2(Ph3P)2 in dioxane (383 K, [BuOH] = 1–8 mol/1). The rates of accumulation of the regioisomeric reaction products as empirical functions of CO pressure and concentrations of styrene, triphenylphosphine, and the catalyst were found. The acyl complex (PhC2H4CO)PdCl(Ph3P)2 was isolated from the reaction mixture. The assumed intermediate of an alcoholate mechanism, the (BuOOC)PdCl(Ph3P)2 complex, is not formed by the reaction of PdCl2(Ph3P)2 with CO and butanol. The set of data generally corresponds to a hydride mechanism of styrene hydrocarboxylation, which includes three key intermediates HPdCIL2-n(CO)n (n= 0–2). A change in the solvation properties of the reaction medium due to the replacement of water by butanol affects the kinetic scheme of the process.

The effect of the composition of the catalytic system Pd(dba)(2)/n HX/8 Ph3P (dba is dibenzylidentacetone) on the yield and ratio of the regioisomeric products of the reaction of styrene with CO and BuOH in dioxane was studied. In comparable conditions, the catalytic activity varies in the order: X = ClO4 greater than or equal to CF3SO3 reversible arrow TsO reversible arrow Cl > > BF4 > > CF3COO. At X = ClO4, TsO, and CF3SO3, increase in the selectivity of the process ill butyl 3-phenylpropanoate is observed at the same or increased catalytic activity. The varied selectivity of the catalytic systems is explained in terms of formation of cationic palladium hydride intermediates.