New catalytic systems based on fluorine-containing titanium(iv) alkoxides for the synthesis of ultrahigh-molecular-weight polyethylene and olefin elastomers

The catalytic activity of the systems based on titanium(iv) alkoxides (Ti(OPrⁱ)₄, Ti(OPrⁱ)₂(OCH(CF₃)₂)₂, and Ti(OCH(CF₃)₂)₄) and mixtures of alkylaluminum chlorides (Et₂AlCl or Et₃Al₂Cl₃) with dibutylmagnesium in ethylene polymerization and ethylene copolymerization with propylene and 5-ethylidene-2-norbornene was studied. Ultrahigh-molecular-weight polyethylene with the molecular weight reaching 4.9 · 10⁶ Da was found to be formed in the homopolymerization reaction, whereas copolymerization gives ter-copolymers containing propylene (up to 35 mol.%) and 5-ethylidene-2-norbornene (4.3 mol.%) units.

     

PASE synthesis of 1-azolyl-1H-1,2,4-triazoles by the reaction of diazoazoles with ethyl isocyanoacetate

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α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization

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Pericyclic reactions in the synthesis of new 5-aryl-5,6-dihydroquinolino[2,1-b]quinazolin-12-ones

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Trimetallic NiCoM catalysts (M = Mn,Fe, Cu) for methane conversion into synthesis gas

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Real-Space Interpretation of Interatomic Charge Transfer and Electron Exchange Effects by Combining Static and Kinetic Potentials and Associated Vector Fields**

Intricate behaviour of one-electron potentials from the Euler equation for electron density and corresponding gradient force fields in crystals was studied. Channels of locally enhanced kinetic potential and corresponding saddle Lagrange points were found between chemically bonded atoms. Superposition of electrostatic and kinetic potentials and electron density allowed partitioning any molecules and crystals into atomic - and potential-based -basins; -basins explicitly account for the electron exchange effect, which is missed for -ones. Phenomena of interatomic charge transfer and related electron exchange were explained in terms of space gaps between zero-flux surfaces of - and -basins. The gap between - and -basins represents the charge transfer, while the gap between - and -basins is a real-space manifestation of sharing the transferred electrons caused by the static exchange and kinetic effects as a response against the electron transfer. The regularity describing relative positions of -, -, and - basin boundaries between interacting atoms was proposed. The position of -boundary between - and -ones within an electron occupier atom determines the extent of transferred electron sharing. The stronger an H⋅⋅⋅O hydrogen bond is, the deeper hydrogen atom's -basin penetrates oxygen atom's -basin, while for covalent bonds a -boundary closely approaches a -one indicating almost complete sharing of the transferred electrons. In the case of ionic bonds, the same region corresponds to electron pairing within the -basin of an electron occupier atom.     

Two Types of σ-Allenyl Complexes from Reactions of Silylenes and Germylenes with Chromium Fischer Alkynyl(alkoxy)carbenes

The reactivity of amidinatotetrylenes of the type E(tBu₂bzm)R¹ (E=Si, Ge; tBu₂bzm=N,N′-bis(tertbutyl)benzamidinate; R¹=alkyl or aryl) with the chromium Fischer alkynylcarbene complexes [Cr{C(OEt)C₂R²}(CO)₅] (R²=Ph; ferrocenyl, Fc) has been studied. At room temperature, two different reaction pathways have been identified: (a) attack of the amidinatotetrylene to the alkynyl C² atom (γ-attack), which leads to σ-allenyl complexes in which the original C_carbene atom maintains its attachment to the Cr(CO)₅ and OEt groups (compounds 3 ), and (b) attack of the amidinatotetrylene to the C_carbene atom (α-attack), which ends in σ-allenyl complexes in which the original C_carbene atom is not attached to the metal atom and has been inserted into an E−N bond of the amidinatotetrylene forming an E-C-N-C-N five-membered ring (compounds 4 ). It has been found that compounds 3 are thermodynamically less stable than their corresponding 4 isomers and that some of the former (E=Ge; R¹=CH₂SiMe₃) can be transformed into the latter upon heating. At high temperatures (>70 °C) the reactions involving bulky amidinatotetrylenes (R¹=Mes, tBu) end in the carbene-substitution products [Cr{E(tBu₂bzm)R¹}(CO)₅].     

Synthesis and rheological properties of star-shaped polydimethylsiloxanes based on carbosilane dendrimers

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Scaling law analysis of electrohydrodynamics and dielectrophoresis for isomotive dielectrophoresis microfluidic devices

Isomotive dielectrophoresis (isoDEP) is a unique DEP geometrical configuration where the gradient of the field-squared () is constant. IsoDEP analyzes polarizable particles based on their magnitude and direction of translation. Particle translation is a function of the polarizability of both the particles and suspending medium, the particles’ size and shape, and the frequency of the electric field. However, other electrokinetics act on the particles simultaneously, including electrothermal hydrodynamics. Hence, to maximize the DEP force relative to over electrokinetic forces, design parameters such as microchannel geometry, fabrication materials, and applied electric field must be properly tuned. In this work, scaling law analyses were developed to derive design rules, relative to particle diameter, to reduce unwanted electrothermal hydrodynamics relative to DEP-induced particle translation. For a particle suspended in 10 mS/m media, if the channel width and height are below ten particle diameters, the electrothermal-driven flow is reduced by ∼500 times compared to a channel that is 250 particles diameters in width and height. Replacing glass with silicon as the device's underlying substrate for an insulative-based isoDEP reduces the electrothermal induced flow approximately 20 times less.