Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”

The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH₂P(t-C₄H₉)₂)₂C₆H₄) and acidic [LWH(CO)₃] (L = Cp (1a), Tp (1b); Cp = η⁵-cyclopentadienyl, Tp = κ³-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] (4a, 4b), which catalyze amine-borane (Me₂NHBH₃, ^tBuNH₂BH₃) dehydrogenation. The combination of variable-temperature (¹H, ³¹P{¹H}, ¹¹B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η¹-borane complex [(PCP)Pd(Me₂NHBH₃)]⁺[LW(CO₃)]⁻ (5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species 4 are easily regenerated through hydrogen evolution in the reaction between two hydrides.

Bimetallic complexes [LW(CO)₂(μ-CO)⋯Pd(PCP)] cooperatively activate amine-boranes for their dehydrogenation via N–H proton tunneling at RDS and H₂ evolution from two neutral hydrides.     

Texture–Strength Properties of the Alumina–Montmorillonite Composite

The texture characteristics and strength properties of the molded alumina–montmorillonite composite are studied. The mixture is obtained by mixing suspensions of activated clay and pseudoboehmite followed by drying (at 293 and 393 K) and calcination (at 873 K). It is a promising support for cracking and hydrotreating catalysts. The changes in the specific surface area; the volumes of micro-, meso-, macropore, and medium-size pores; and the strength of samples are studied by varying the montmorillonite concentration in the composite. The addition of 20–35 wt % clay largely results in a sharp in reduction of the macropore region and, correspondingly, provides the alumina oxide average strength of the extrudates of 10–12 MN/m², which is sufficient for industrial supports. This excludes the stage of standard acidic peptization from the technological scheme of alumina production. The complex study of the porous structure of the composite by adsorption and mercury porosimetry combined with elements of percolation theory makes it possible to predict the texture–strength properties of derivative materials.     

Palladium hydrogenation catalyst based on a porous carbon material obtained upon the dehydrochlorination of a chloro polymer

The applicability of a porous carbon material obtained as a result of the “chemical” dehydrochlorination of chlorinated polyvinyl chloride as a support for palladium hydrogenation catalysts was demonstrated. The efficiency of the catalyst was evaluated in the liquid-phase reactions of nitrobenzene hydrogenation and chlorobenzene hydrodechlorination. Although the specific activity of the catalyst was lower by a factor of 3–4 than that of the samples based on Sibunit and carbon nanotubes, the complete conversion of the initial compounds with the selective formation of end products under mild conditions was achieved at a relatively low palladium content (1.5%).     

(CuO-CeO2)/glass cloth catalysts for selective CO oxidation in the presence of H2: The effect of the nature of the fuel component used in their surface self-propagating high-temperature synthesis on their properties

The potential of surface self-propagating high-temperature synthesis (SSHS) for obtaining (CuO-CeO₂)/glass cloth catalysts is demonstrated. The dependence of the structural and catalytic properties of the catalysts on their preparation conditions (nature of the fuel component) is considered. X-ray diffraction, electron microscopy, and EXAFS data suggest that the short-term action of high temperature in the SSHS leads to the complete decomposition of the precursors and has an effect on the distribution of the resulting phases. According to H₂ TPR and XPS data, the degree of dispersion of CuO and the electronic state of the reacting CuO and CeO₂ phases depend on the choice of fuel. This is likely due to fuels varying in the amount of heat released in their combustion. The degree of dispersion of CuO and the total contribution from Cu¹⁺ and Ce⁴⁺ to the electronic state of the active component increase as the standard enthalpy of combustion increases in the urea < glycerol < citric acid order. This leads to an increase in the catalytic activity of the (CuO-CeO₂)/glass cloth system in selective CO oxidation.     

Structure of the Mo-Containing Dispersed Catalyst During Heavy Oil Upgrading in the Presence of Steam And Hydrogen

XRD, TEM, EXAFS/XANES methods are first used to study the structure and morphology of Mocontaining phases of carbon residues of heavy oil refining during catalytic steam cracking, catalytic cracking without water, and hydrocracking. According to the results obtained from physical and chemical studies of Mo-based catalytic phases, the reaction medium affects structural features of Mo-containing phases, e.g. the amount of oxide and sulphide forms, the particle size, and particle morphology.     

Catalysts Pt/(Ga)Al2O3 Obtained Using Aluminum Metal Activated with Gallium

Russian Journal of Applied Chemistry - The products of the interaction of activated aluminum with water were used as a precursor of an oxide support of catalysts. The possibility of changing the...     

Synthesis of Mg<Superscript>2+</Superscript>-, Al<Superscript>3+</Superscript>-, and Ga<Superscript>3+</Superscript>-containing layered hydroxides and supported platinum catalysts based thereon

The effect of the cationic composition of MgAl(Ga) layered double hydroxides on the structure, texture, and acid–base properties of related oxide supports for platinum catalysts has been investigated. As gallium is progressively substituted for aluminum in the mixed oxide, the properties of the support change only slightly, while the activity of the Ga–Pt catalysts in propane conversion increases, the propylene selectivity remains high (99%), and C–C bond hydrogenolysis is hampered.     

Polarity and Conformatios of Phosphorylethylenes and Phosphorylacetates in Solution

Abstract

A series of derivatives R¹R²P(X)R³, where R¹=R²=Ph. R³= -CH=CH-Me, X=O(I); R¹=Me, R²=Ph, R³= -CH=CH₂, X=O(II); R¹=R²=Ph, R³= -CH=CH₂, X=Se(III) and R¹R²P(O)-CH₂C(O)OX, where R¹=Ph, R²= -CH=CH₂, X=Ment?(IV); R¹=Ph-2-OMe, R²=Ph, X=Ment?(V); R¹=R²=CH₂Ph, X=Et(I), were investigated by means of dipole moments method. The problem of conjugation in phosphorylethylenes and conformation behaviour of phosphorylacetates was considered. DM (exp.) of (I-IV), determined in CC1₄ solution are 4.48(I), 4.27(II), 4.97(III), 4.21(IV), 5.21(V) and 4.02 D (VI). The intramolecular electronic interactions of phosphoryl group with unsaturated fragment did not displays in polarity properties of compounds (I-III). The experimental dipole moments of derivatives (I-III) are equal to the calculated values of DM. DM (IV-VI) is very sensitive to orientation of the P=O and C=O polar bonds. Because DM (exp.) of these compounds very sensitive to its orientation. DM (calc.) for cis- and trans- orientation of P=O and C=O dipoles are really different, that allows to drow the conclution that, in the contrast to the crystal state, the corresponded dipoles prefer an anti array in solution.     

Cold crystallization kinetics of slag from the joint smelting of oxidized nickel and sulfide copper ores

Journal of Thermal Analysis and Calorimetry - The cold crystallization kinetics of the glass-crystal composition (90.3 vol% of glass) made of slag from the joint smelting of oxidized nickel and...     

Data acquisition system for the socal plane detector of the mass separator MASHA

The results of the development and the general information about the data acquisition system which was recently created at the MASHA setup (Flerov laboratory of nuclear reactions at Joint institute for nuclear research) are presented. The main difference from the previous system is that we use a new modern platform, National Instruments PXI with XIA multichannel high-speed digitizers (250 MHz 12 bit 16 channels). At this moment system has 448 spectrometric channels. The software and its features for the data acquisition and analysis are also described. The new DAQ system expands precision measuring capabilities of alpha decays and spontaneous fission at the focal plane position-sensitive silicon strip detector which, in turn, increases the capabilities of the setup in such a field as low-yield registration of elements.