Some spectroscopic and freezing point depression measurements on the homogeneous hydrogenation catalyst CoH3(PPh3)3

NMR, EPR and freezing point depression (FPD) experiments were performed on solutions of the homogeneous hydrogenation catalyst CoH₃(PPh₃)₃. The results of these measurements show that the compound has a dynamic structure on the NMR time scale at room temperature and that it is slightly dissociated into bisphosphine species and free phosphine. FPD and¹H-NMR measurements indicate that one Et₂O molecule is present per catalyst molecule.

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, () CoH₃(PPh₃)₃. , , . H¹- , Et₂O.

     

Rate constant of unimolecular decomposition of the radical (CH3)2juvyCCH(CH3)2

The energy of activation of CH ₃ ^. radical rupture from the radical (CH₃)₂juvyCCH(CH₃)₂ is 142.2 kJ mol^–1; the selfcombination rate constant is k_c {(CH₃)₂juvyCCH(CH₃)₂}=10^7.3 dm³ mol^–1 s^–1.

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CH ₃ ^. (CH₃)₂juvyCCH(CH₃)₂ 142,2 /, k_c {(CH₃)₂juvyCCH(CH₃)₂}=10^{7,3 3–1 –1}.

     

[Fe(phen)3]2+ aquation in aqueous polyacrylamide solution

The aquation of tris(1, 10-phenanthroline) iron(II) has been studied in aqueous polyacrylamide solutions. The rate increases up to 2.8 times at low polymer concentrations, and subsequently decreases. These effects are attributed to changes in the local water activity in the region of the complex.

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(1, 10-) (II) . 2,8 , . .

     

The compound Rh[HN((CH2)3P(C6H5)2)2]Cl in a hydrogenation reaction

The tridentate chelate ligand bis(diphenylphosphinopropyl) amine and its title complex were prepared and characterized by³¹P n.m.r. and other spectroscopic data. Its activation energy E_A for hydrogenation of cyclohexene is 52.3 kJ mol^–1.

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³¹P. 52,3 /.

     

Synthesis and studies of catalysts prepared by supporting Hf(CH2Ph)4 on SiO2 and Al2O3

Catalysts prepared by supporting Hf(CH₂Ph)₄ on silica and alumina were studied. Their catalytic activity in ethylene polymerization was shown to increase considerably upon heating in hydrogen. IR spectroscopic studies of catalysts heated in hydrogen show the formation of surface Hf hydrides.

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, Hf (CH₂Ph)₄ . , . .

     

ESR studies of T3+ complexes formed in the catalytic system TiCl2(acac)1+Et2AlCl and their interaction with ethylene, carbon monoxide and pyridine

Coordination state of Ti³⁺ions formed in the homogeneous catalytic systems TiCl₂(acac)₂+Et₂AlCl, and its changes upon interaction with ethylene, carbon monoxide and pyridine have been studied by ESR.

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Ti³⁺, TiCl₂(acac)₂=Et₂AlCl, , .

     

Catalytic properties of Cu(Acac)2 anchored to shock-compressed MgO and MgF2 supports

Catalytic properties of Cu(Acac)₂ anchored to shock-compressed MgO and MgF₂ in model reactions of hydrogenation and isomerization of heptene-1 have been studied. It is shown that by changing the defect structure of the support via shock treatment at various temperatures, the activity and selectivity of metal complex catalysts can be affected.

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Cu(Acac)₂, MgO MgF₂ -1. , , , .

     

Structure, activity and selectivity of V2O5-TiO2 catalysts for o-xylene conversion

The formation of needle shaped crystallites of V₆O₁₃ at low V concentrations on V₂O₅-anatase coated catalysts explains the low selectivity for phthalic anhydride during o-xylene oxidation. The (010) plane of V-oxide, most active for selective oxidation of o-xylene, is not accessible and the contact of this plane with the anatase faces promotes the anatase-rutile transformation and the incorporation and blocking of V⁴⁺ ions.

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V₆O₁₃ V , V₂O₅-, -. (010) , -, , - V⁺⁴.

     

Kinetics of ethylene oxidation to EGMA in the presence of PdCl2 and Fe(NO3)3

Kinetic regularities of ethylene oxidation to ethylene glycol monoacetate (EGMA) in the presence of a PdCl₂ and Fe(NO₃)₃-containing catalytic system has been studied to clarify the peculiarities of the mechanism of this reaction.

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() .

     

Catalytic activity of the Al2O3?Cr2O3?Fe2O3 system II. Influence of nitrogen bases on hydrocarbon aromatization

The physico-chemical properties of the Al₂O₃–Cr₂O₃–Fe₂O₃ catalyst system have been correlated with n-hexane dehydrocyclization. Using a poisoning technique, the ionic and radical steps of the reaction have been determined.

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- Al₂O₃–Cr₂O₃–Fe₂O₃ -. , .

     

Catalysts for metathesis of olefins, prepared by anchoring of MoO2(acac)2 to Al2O3

New highly active catalysts for metathesis of olefins were obtained through the interaction of bis(acetylacetonato)dioxymolybdenum(VI) with surface OH groups of -Al₂O₃ and subsequent reduction in H₂ or CO.

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()(VI) OH -Al₂O₃ H₂ CO .

     

CO oxidation over CuCr/Al2O3 catalysts in presence of SO2

Poisoning of variously prepared CuCr/Al₂O₃ catalysts having different compositions by sulfur dioxide has been studied. Comparative values for a decrease in the catalyst activities have been obtained.

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CO .

     

XPS study of the in-depth profile of TiO2?Al2O3 catalysts prepared by different methods

An XPS study of in-depth profiles of Ti/Al ratio in TiO₂–Al₂O₃ catalysts in conjunction with sputter-etching by Ar⁺ has revealed that the sample prepared with ammonia as precipitation reagent has constant Ti/Al ratio from surface layer to bulk, while the smaple prepared with urea has much Al in the surface layer.

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Ti/Al TiO₂–Al₂O₃ Ar⁺ , , , Ti/Al , , , .

     

Unsteady-state performance of NOx catalytic reduction by NH3

Experimental results of studying NO_x catalytic reduction by NH₃ under periodic reversals in the direction of filtration of the mixture purified in a catalyst bed are discussed.

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NO_x .

     

State of components in contact solutions based on Pd(II) salts and Fe(NO3)3 for ethylene oxidation to EGMA

Physico-chemical studies of contact solutions based on Pd(II) salts and Fe(NO₃)₃ for ethylene oxidation to EGMA have been carried out.

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- (II) .

     

Electrocatalytic properties of the Ti(OH)3?Mo(III) system in the reduction of molecular nitrogen

Electrochemical reduction studies of dinitrogen catalyzed by Ti(OH)₃–Mo(III) in an alkaline methanol solution on a mercury cathode show that the maximum yield of hydrazine (4%) and ammonia (43%) is observed at 0.5 mA/cm² current density. In experimental conditions it corresponds to the zero-charge potential of sodium amalgam (–1.86 V).

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, T (OH)₃–Mo(III), , (43%) (4%) 0.5 mA/cm², .

     

New model of the hydroxylating enzyme system of liver microsomes: NADH-riboflavine-hemoglobin-O2

The kinetics of aniline hydroxylation to p-aminophenol by the NADH-riboflavine-hemoglobin-O₂ system has been investigated in a phosphate buffer (pH 6.8) at 37°C. At optimal concentrations of the model system components the rates of aniline oxidation are comparable with those of the enzymatic hydroxylation of aniline by rat liver microsomes. Possible paths of aniline hydroxylation in the system NADH-riboflavine-hemoglobin-O₂ are discussed.

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37°C pH 6,8 - .---O₂. . .---O₂.

     

Study of cyclohexane conversion on A Pt/Al2O3 catalyst under reforming conditions by a gradientless method

A common type of rate equations for hydrocarbon conversions under reforming conditions has been shown, resulting from the features of the hydrocarbons and hydrogen adsorption on the Pt/Al₂O₃ catalyst. This has been confirmed by variations in the rate of cyclohexane conversion observed upon the introduction of methane into the reaction mixture. Methane does not react but is strongly adsorbed on the catalyst surface.

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, . , , .

     

XPS study on the decomposition of Ru3(CO)12 and Fe3(CO)12 carbonyl clusters

Crystalline Ru₃(CO)₁₂ and Fe₃(CO)₁₂ carbonyl clusters were deposited on a Cu sample holder and core level binding energies (BE) for O 1s, C 1s Fe 2p 3/2, Fe 2p 1/2, Ru 3d 5/2 and Ru 3d 3/2 were measured before and after decomposition. Part of the carbonyl clusters remained in the original form even at a pressure of 10^–5 Pa, indicated by a Fe satellite peak and high BE for C 1s. After decomposition, carbon is partly retained by iron, whereas the twin peak at Ru 3d 5/2 and Ru 3d 3/2 show no carbon left on the ruthenium surface.

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Ru₃(CO)₁₂ Fe₃(CO)₁₂ (BE) O 1S, C 1S, Fe 2p 3/2, Fe 2p 1/2, Ru 3d 5/2 Ru 3d 3/2 . 10^–5 Pa, Fe BE 1S. , Ru 3d 5/2 Ru 3d 3/2 , .

     

Conversion of hydrocarbons on supported catalysts prepared via decomposition of surface complexes. Preparation and properties of (Ga+Pt)/SiO2 and (Ga+Pt)/Al2O3 catalysts

The addition of gallium is shown to increase Pt dispersity and its stability to deactivation in n-hexane dehydrocyclization, to decrease the rate of n-hexane hydrogenolysis and to increase the selectivity to benzene, apparently, due to the interaction of Pt clusters with surface Ga ions.

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, -, - . .