4,4-Diorganyl-1,1,3,6-tetrachloro-1,4-tellura(IV)silafulvenes - New class of tellurium-silicon containing heterocycles

The reaction of TeCl₄ with diorganyl diethynyl silanes RR¹Si(CCH)₂ in CHCl₃ at room temperature leads to regio- and stereoselective formation of a new class of unsaturated five-membered heterocycles, 4,4-diorganyl-1,1,3,6-tetrachloro-1,4-tellura(IV)silafulvenes, in high yields. In the case of dialkyl substituents at the silicon atom the reaction proceeds with 100% stereoselectively to afford only E-isomers, while for cyclic diethynyl silanes the spiro-heterocycles formed have Z- and E-configurations, E-isomers being the predominant ones. Structures of the heterocycles have been proved by the multinuclear (¹H, ¹³C, ²⁹Si, ¹²⁵Te) NMR spectroscopy, 2D NOESY NMR spectroscopy and mass-spectrometry. Z-Isomers are characterized by a long-range spin-spin interaction of protons through five bonds with ⁵J_HH 0.2-0.5 Hz lacking in E-isomers. In the mass spectra the heterocycles manifest themselves as the fragment ions [M−Cl₂]⁺.     

Oxidation of cycloalkanones with hydrogen peroxide: an alternative route to the Baeyer-Villiger reaction. Synthesis of dicarboxylic acid esters

The acid-catalyzed oxidation of cycloalkanones C₅-C₈ and C₁₂ with hydrogen peroxide in alcohols was performed, and dicarboxylic acid esters were obtained as the major products in 53-70% yields. In the first step, geminal bishydroperoxides are generated from five-to-seven-membered cyclic ketones. The Baeyer-Villiger reaction is a side process accompanied by the formation of ω-hydroxycarboxylic acid esters.     

A Novel Tantalum Cluster Chalcohalide Ta4S1.5Se7.5I8

Single crystals of Ta₄S_1.5Se_7.5I₈ are obtained by heating Ta, S, Se and I₂ at 300 °C in 4.0:1.0:8.0:4.4 molar ratio. The structure was determined by X-ray analysis and consists of molecular clusters [Ta₄(μ₄-S)(μ₂-Q_axSe_eq)₄I₈] (Q ≈ Se_0.87S_0.13). The tantalum atoms form a square with long Ta…Ta distances (3.26–3.32 Å), with four dichalcogenide ligands bridging the Ta–Ta edges and a sulfur atom capping the square. Each Ta atom has two terminal iodine atoms. Raman spectroscopy study shows the presence of the characteristic absorption band at 396 cm^?1 which is due to the Ta₄–μ₄-S vibrations. Cyclic voltammetry shows that Ta₄S_1.5Se_7.5I₈ in solid state undergoes quasi-reversible one-electron oxidation which is metal-centered.     

Collisionally assisted spectroscopy of water from 27,000 to 34,000 cm(-1)

We report here an experimental approach that enables measurement of weak transitions to a wide range of rovibrational levels of water in the energy region 27,000-34,200 cm(-1). We have previously demonstrated the use of laser double-resonance overtone excitation to access highly excited vibrational levels from single rovibrational states. Although this approach simplifies the assignment of the spectra, it strongly reduces the number of observed transitions and hence our ability to test theoretical predictions. Here, we increase significantly the number of observed transitions by allowing rotational relaxation of H2O at intermediate levels of the double-resonance excitation scheme to the levels of the same nuclear spin (ortho or para). Our recently developed semiempirical potential energy surface PES12 enables assignment of the resulting complex spectra and reproduction of the measured transitions with accuracy better than 1 cm(-1).     

Ionic liquid near a charged wall: structure and capacitance of electrical double layer

We study the effects of ion size asymmetry and short-range correlations on the electrical double layer in ionic liquids: we perform molecular dynamics simulations of a model ionic liquid between two "electrodes" and calculate the differential capacitance of each as a function of the electrode potential. The capacitance curve has an asymmetric "bell-shape" character, in qualitative agreement with recent experiments and the mean- field theory (MFT) which takes into account the limitation on the maximal local density of ions. The short-range ionic correlations, not included in the MFT, lead to an overscreening effect which changes radically the structure of the double layer at small and moderate charging. With the radius of cations taken to be twice as large as anions, the position of the main capacitance maximum is shifted positively from the potential of zero charge (PZC), as predicted by MFT. An extension of the theory (EMFT), however, reproduces the simulated capacitance curve almost quantitatively. Capacitance curves for real ionic liquids will be affected by nonspherical shape of ions and sophisticated pair potentials, varying from liquid to liquid. But understanding the capacitance behavior of such model system is a basis for rationalizing those more specific features.     

Reactivity of Pt- and Pd-bound nitriles towards nitrile oxides and nitrones: substitution vs. cycloaddition

Reactions of the nitrone CH3CH=N(CH3)O and the nitrile oxide CH3C[triple bond]NO with the nitrile complexes trans-[MCl2(N[triple bond]CCH3)2] (M = Pt, 1; Pd, 2) were investigated by theoretical methods at B3LYP and, for some processes, CCSD(T) levels of theory. The mechanisms of substitutions and cycloadditions were studied in detail. The former occur via a concerted asynchronous mechanism of dissociative type. The calculations of the metal-ligand bond energies in the starting complexes and substitution products and the analysis of structural features of the transition states indicate that the M-N bond dissociation (rather than M-O bond formation) is the step, which controls the reactivity of and in substitutions. The different chemical behaviours of the Pt and Pd complexes towards the 1,3-dipoles were investigated. The exclusive isolation of cycloaddition rather than substitution products in any solvents in the case of is both kinetically and thermodynamically controlled.The switch of the reaction mode from cycloaddition to substitution for 2 in CH2Cl2 solution is caused by the significantly lower Pd-N bond energy in comparison with the Pt-N bond energy, consistent with the higher lability of the Pd complexes. The different chemical behaviour of 2 in CH3CN and CH2Cl2 solvents is accounted for by the great excess of acetonitrile in the CH3CN solution rather than a different solvation character. The relative variation of Wiberg bond indices along the reaction path is proposed as a quantitative criterion for the classification of the reaction mechanism.     

Twin families of bisolitons in dispersion-managed systems

We calculate bisoliton solutions by using a slowly varying stroboscopic equation. The system is characterized in terms of a single dimensionless parameter. We find two branches of solutions and describe the structure of the tails for the lower-branch solutions.     

Particle physics catalysis of thermal big bang nucleosynthesis

We point out that the existence of metastable, tau>10(3) s, negatively charged electroweak-scale particles (X-) alters the predictions for lithium and other primordial elemental abundances for A>4 via the formation of bound states with nuclei during big bang nucleosynthesis. In particular, we show that the bound states of X- with helium, formed at temperatures of about T=10(8) K, lead to the catalytic enhancement of 6Li production, which is 8 orders of magnitude more efficient than the standard channel. In particle physics models where subsequent decay of X- does not lead to large nonthermal big bang nucleosynthesis effects, this directly translates to the level of sensitivity to the number density of long-lived X- particles (tau>10(5) s) relative to entropy of nX-/s less, approximately <3x10(-17), which is one of the most stringent probes of electroweak scale remnants known to date.     

Novel electroosmotic micromixer configuration based on ion-selective microsphere

In this paper, a micromixer of a new configuration is presented, consisting of a spherical chamber in the center of which an ion-selective microsphere is placed. Stratified liquid is introduced through the chamber via inlet and outlet holes under an external pressure gradient and an external electric field is directed in such a way that the resulting electroosmotic flow is directed against the pressure-driven flow, resulting in mixing. The investigation is carried out by direct numerical simulation on a super-computer. Optimal values of the applied electric field are determined to yield strong mixing. Above this optimal mixing regime, a number of instabilities and bifurcations are realized, which qualitatively coincide with those occurring during electrophoresis of an ion-selective microgranule. As shown by our calculation, these instabilities do not lead to an enhanced mixing. The resulting electroconvective vortices remain confined near the surface of the microgranule, and do not sufficiently perturb the stratified fluid flow further from the granule. On the other hand, another type of instability caused by the salt concentration gradient can generate sufficiently strong oscillations to enhance mixing. However, this only occurs when the external electric field is sufficiently high that the electroosmotic flow is comparable to the pressure-driven flow. This ultimately leads to creation of reverse flows of the liquid and cessation of the device operation. Thus, it was shown that the best mixing occurs in the absence of electrokinetic instability. Based on the data obtained, it is possible to select the necessary geometric characteristics of the micromixer to achieve the optimal mixing mode for a given set of liquids, which may be ten times more effective than passive mixers at the same flow rates. A comparison with the experimental data of the other authors confirms the effectiveness of this device and its other capabilities. Furthermore, the basic device design can be operated in other modes, for example, an electrohydrodynamic pump, a streaming current generator, or even a micro-reactor, depending on the system parameters and choice of an ion-selective granule.