Effect of the composition of (Mo,Nb, V,Ti)/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surface oxide structures on the oxidative dehydrogenation of ethane to ethylene

Molecular layering method was used to synthesize on the surface of γ-Al₂O₃ vanadium-titanium oxide structures of varied composition and structure from the gas phase and niobium- and molybdenum-containing additives from the liquid phase. The resulting composites and the starting aluminum oxide were studied by X-ray diffraction analysis and chemical-analytical and adsorption methods. The catalytic properties of the synthesized products were examined in the oxidative dehydrogenation of ethane. It was shown that the activity of the samples is affected not only by the composition and structure of surface structures, but also by the relative amounts of components in mechanical mixing of vanadium-titanium oxide and niobium oxide supported systems.     

What is the Nature of the First‐Formed Intermediates in the Electrophilic Halogenation of Alkenes,Alkynes, and Allenes?

The pi complexes first formed as essential intermediates from alkenes, alkynes, and allenes with bromine have been investigated in different solvents by UV-spectroscopy in combination with stopped-flow techniques allowing the determination of the equilibrium constants, K(f). Using alkenes with sterically protected double bonds, such as di-tert-butylstilbene and tetraneopentylethylene, the reaction stops at the stage of the 1:1 and 1:2 pi complex of the alkene with bromine as persistent species in 1,2-dichlorethane as solvent. Calculations by state-of-art ab initio and DFT methods reproduces the experimentally determined thermodynamic values quite well, and reveal the preferred structures and nature of both complexes for ethene, ethyne, and allene. Consideration of the entropy term reveals that complexes are stabilized in solution owing to reduction of the entropy loss by restricted translations and rotation. According to calculations these species are Mulliken-outer-type complexes with no or little charge transfer from bromine to the double or triple bond, respectively. The 1:2 complex has a close structural relationship to the bromonium- or bromirenium ion, which is the subsequent intermediate on the reaction coordinate. Steric influences show a strong effect on the K(f) value, which can be explained by the polarizibility of the parent system. Addition-elimination often occurs. In bromination of adamantylidenadamantane and its derivatives the reaction stops at the stage of the bromonium ion. The effect of various polar groups situated in equatorial homoallyl positions on the stability of corresponding pi complex and bromonium ion has been studied in this series.     

An investigation of the scope of the 1,7-electrocyclization of α,β:γ,δ-conjugated azomethine ylides

Substituents on the diene component have little influence on the periselectivity of the cyclizations of α,β:γ,δ-conjugated azomethine ylides, with 1,7-electrocyclizations predominating. In some cases, subtle changes to these substituents can, however, influence the product formed, through their effect on the relative energies of the transition states for the 1,5- (6π) and 1,7-electrocyclization (8π) processes. The most striking changes in periselectivity occur for phenylethenyl-substituted azomethine ylides 3d–f, which can give either a pyrroline 4d,f or dihydrobenzazepine 6e, depending upon the alkene configuration.     

Catalytic properties of α-U3O8 in dehydrogenation and dehydration; the energies of the bonds of carbon,hydrogen, and oxygen with the catalyst

Russian Chemical Bulletin -     

Study of the formation temperature of mixed LaREO<Subscript>3</Subscript> (RE ≡ Dy,Ho, Er,Tm, Yb,Lu) and NdGdO<Subscript>3</Subscript> oxides

Mixed LaREO₃ (RE ≡ Dy, Ho, Er, Tm, Yb, Lu) and NdGdO₃ oxides were prepared by thermal decomposition of the corresponding co-precipitated mixed oxalates. The decomposition of La/RE and Nd/Gd oxalates was studied by means of differential thermal analysis and thermogravimetric (DTA-TG) measurements; in particular the last step, consisting of the loss of a CO₂ molecule from the corresponding oxycarbonate, has been thoroughly investigated, as it is particularly interesting for the study of the formation temperature of mixed rare earth oxides. After the release of CO₂, the oxides crystallize in a distorted perovskitic cell or one of the structures typical of rare earth sesquioxides, depending on the cationic size difference and on the average cationic radius. The mixed rare earth oxycarbonate decomposition has been studied in comparison to the decomposition of single rare earth oxycarbonates. A trend of the mixed oxides formation temperature as a function both of the average cationic size and of the cationic sizes difference has been observed and compared to the behaviour of single rare earth oxides.     

Regularities of change in the structural parameters of EuLnCuS<Subscript>3</Subscript> (Ln = La–Nd,Sm, Gd,Ho)

Regularities of change in the structural parameters of EuLnCuS₃ (Ln = La–Nd, Sm, Gd, Ho) at an annealing temperature of 970 and 1170 K have been established. A decrease in the Ln³⁺ ionic radius results in the consecutive change of structural types (STs) for the compounds: α-EuLnCuS₃ (Ln = La, Ce, Pr, Nd; BaLaCuS₃ ST) → β-EuLnCuS₃ (Ln = Ce, Pr, Nd; Ba2MnS₃ ST) → γ-EuLnCuS₃ (Ln = Sm, Gd, Ho; Eu₂CuS₃ST). The change of structural types for EuLnCuS₃ leads to a jump-like change in their unit cell parameters and the transformation of coordination polyhedra shaped as a one-capped trigonal prism LnS₇ (α and β phases) into an octahedron LnS₆ (γ phases). The appearance of morphotropic changes correlates with the tetrad effect.     

Photochemistry of the IrCl<Subscript>6</Subscript><Superscript>2−</Superscript> complex in aqueous solutions in the presence of the bromide anions

Laser flash photolysis (308 nm) was applied to study photochemistry of the IrCl₆ ²⁻ complex in aqueous solutions in the presence of the Br⁻ anions. The formation of the Br₂ ^·− radical anions in the reaction between the Br⁻ ion and secondary radical pair formed after the photon absorption by the initial complex was observed. The Br₂ ^·− radical anions decay both in recombination and in the reaction with the initial IrCl₆ ²⁻ complex.     

Kinetics of the Decomposition of α-Phenylethyl Hydroperoxide in the Presence of <Emphasis Type="Italic">N,N,N′,N′</Emphasis>-Tetramethyl-<Emphasis Type="Italic">para</Emphasis>-Phenylenediamine

It is found that the tertiary amine N,N,N′,N′-tetramethyl-para-phenylenediamine (TMPD) causes the decomposition of α-phenylethyl hydroperoxide (ROOH), and the interaction between the components occurs in accordance with a complicated rate law. It is demonstrated that more than 30 hydroperoxide molecules (n) can be degraded at a molecule of TMPD; this fact suggests that the amine has a catalytic effect on the process. The value of n increases with the [ROOH]₀/[TMPD]₀ ratio. The initial rates of consumption of ROOH and TMPD linearly increase with the initial concentrations of both of the reactants. The apparent rate constant of the reaction is k = 0.4 l mol^?1 s^?1 (393 K), as calculated from the initial rates of ROOH consumption. As a result of the interaction, TMPD is converted into an inhibitor. The rate constant of the reaction of this inhibitor with ethylbenzene peroxy radicals is about 2 × 10⁴ l mol^?1 s^?1.     

Construction of the Skeleton of Phthalascidin, Mechanism of the Formation of the Key Tricyclic Lactam Intermediate

Phthalascidin is a structurally simplified version of Et-743, which is a potent anti-tumor marine natural product isolated from Ecteinascidia turbinata. Its antiproliferative activity is greater than that of the agents taxol, camptothecin, adriamycin, mitomycin C, cisplatin, bleomycin, and etoposide by 1-3 orders of magnitude. An elegant synthesis of Et-743 and phthalascidin has been reported by E. J. Corey and co-workers1,2. As part of our continuing program, we have also engaged in dev…     

Mechanism,reactivity, and selectivity of the iridium-catalyzed C(sp3)–H borylation of chlorosilanes

The iridium-catalyzed C(sp³)–H borylation of methylchlorosilanes is investigated by means of density functional theory, using the B3LYP and M06 functionals. The calculations establish that the resting state of the catalyst is a seven-coordinate Ir(v) species that has to be converted into an Ir(iii)tris(boryl) complex in order to effect the oxidative addition of the C–H bond. This is then followed by a C–B reductive elimination to yield the borylated product, and the catalytic cycle is finally completed by the regeneration of the active catalyst over two facile steps. The two employed functionals give somewhat different conclusions concerning the nature of the rate-determining step, and whether reductive elimination occurs directly or after a prior isomerization of the Ir(v) hydride intermediate complex. The calculations reproduce quite well the experimentally-observed trends in the reactivities of substrates with different substituents. It is demonstrated that the reactivity can be correlated to the Ir–C bond dissociation energies of the corresponding Ir(v) hydride intermediates. The effect of the chlorosilyl group is identified to originate from the α-carbanion-stabilizing effect of the silicon, which is further reinforced by the presence of an electron-withdrawing chlorine substituent. Furthermore, the source of selectivity for the borylation of primary over secondary C(sp³)–H can be explained on a steric basis, by repulsion between the alkyl group and the Ir/ligand moiety. Finally, the difference in the reactivity between C(sp³)–H and C(sp²)–H borylation is investigated and rationalized in terms of distortion/interaction analysis.     

The influence of the organolithium reagent nature on the possibility of the O→C<Subscript>sp</Subscript> migration of the R<Subscript>3</Subscript>Si group in propynes HC≡CCH<Subscript>2</Subscript>OSiR<Subscript>3</Subscript>

A possibility of the O→C_sp 1,4-migration of the R₃Si group in silyl ethers of terminal acetylenic alcohols upon treatment with organolithium reagents (RLi) was studied. In the case of 3-trimethylsilyloxypropyne, depending on the nature of RLi, the heterolysis of the Si—O bond occurs either by the action of acetylide formed as a result of deprotonation with the formation of 3-trimethylsilylprop-2-yn-1-ol trimethylsilyl ether, or by the action of the metalation agent with the formation of propargyl alcohol. The realization of the O→C_sp 1,4-migration of the Me₃Si group requires the use of mild organolithium reagents (lithium hexamethyldisilazanide and diisopropylamide). Silyl ethers having steric hindrance at the carbon atom bonded to the reaction center or around the silicon atom do not react with the studied organolithium reagents.     

Features of high-temperature behavior in NdCaCoO<Subscript>4</Subscript>—the catalyst of the partial oxidation of methane to syngas

The peculiarities of the high-temperature (373–1173 K) behavior and transport properties of NdCaCoO₄, which is a highly active and selective catalyst of the partial oxidation of methane to syngas, were considered. A relationship between its thermal and electrophysical properties and the structure and defectiveness of the oxygen sublattice was found. The electric conductivity of this compound, which is a two-dimensional analog of perovskite, was found to be almost independent of the oxygen pressure (\(p_{O_2 } = 10^{ - 4} - 1\) atm) and to increase with temperature, reaching ～100 S/cm at 1173 K. The temperature dependence of the conductivity of the n-type semiconductor NdCaCoO₄ has two thermoactivation regions (373–573 and 573–873 K), in which the activation energy is almost doubled (0.46 and 0.81 eV, respectively). The discovered tendencies that determine the unique catalytic properties of this material are probably due to the change in the energy spectrum of this compound. The hypothetical reasons for this change are discussed.     

Acuminatanol, the first 2′,2?-bis-dihydrobiflavonol from the aqueous extract of Trichoscypha acuminata

One new 3′,4′,5′,5,7-pentahydroxy-2′,2?-bis-dihydrobiflavonol, acuminatanol (1), was obtained from the aqueous extract of Trichoscypha acuminata. The structure elucidation process was performed primarily utilizing a capillary scale NMR probe. Acuminatanol (1) is the first example of a bis-dihydroflavonol linked exclusively via the B-rings at C-2′ and C-2? positions. To date, it is the first naturally-occurring compound reported from the genus Trichoscypha, and the first new natural product published from our compound libraries generated from the aqueous extracts of American and African plants.