A density functional theory study of rhodium-catalyzed hetero-[5+2]-cycloaddition of cyclopropyl imine derivatives and alkynes

The intermolecular [5+2]-cycloaddition mechanism of cyclopropyl imines and alkynes catalyzed by [Rh(CO)2Cl]2 has been studied using density functional theory, comparing this multistep process with the two-step reaction in the absence of catalyst. Calculations show that a similar mechanism to that found for dihydroazepines could also lead to the formation of oxepines by replacing the imine nitrogen by oxygen. The results indicate that the formation of the oxepine can proceed with smaller barriers than those found for dihydroazepines. In fact, energy barriers are even smaller than those for other reactions employed for oxepine production, exhibiting values similar to those obtained for the reactions between acetilene and vinylcyclopropanes. Several substituted alkynes were tested for the reaction leading to no significant differences among them.     

A theoretical study of pericyclic rearrangements catalyzed by lithium

The role of lithium cation in the isomerization from diademane to triquinacene and in the Claisen reaction from phenyl allyl ether to 6-allyl-2,4-cyclohexadienone was analyzed. The nature of the interaction of the lithium ion with the reacting molecules in the transition state was studied using supermolecule and perturbational methods. The aromaticity of the transition state in presence of lithium was compared with that for the same reaction in absence of catalyst, employing tools such as nucleus-independent chemical shift and anisotropy of the induced current density. Our results support that the catalytic effect is caused principally by a more favorable electrostatic interaction of lithium cation with the transition states of both reactions.     

Adsorption of phenylphosphonic acid on GaAs (100) surfaces

The adsorption of phenylphosphonic acid (PPA) on GaAs (100) surfaces from solutions in acetonitrile/water mixtures was studied using Fourier transform infrared spectroscopy in attenuated total reflection in multiple internal reflections (ATR/MIR), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS), and atomic force microscopy (AFM). ATR/MIR in situ showed that the accumulation of PPA molecules near the GaAs surface increased with the water concentration in the solution. For water contents lower than 4%, ATR/MIR and XPS results are consistent with the formation of a low-density monolayer. A mechanism is proposed for H2O percentages lower than 4% involving the creation of interfacial bonds through a Br?nsted acid-base reaction, which involves the surface hydroxyl groups most probably bound to Ga. It was found that the morphology of the final layer depended strongly on the water concentration in the adsorbing solution. For water concentrations equal to or higher than 5%, the amount of adsorbed molecules drastically increased and was accompanied by modifications in the infrared spectral region corresponding to P-O and P=O. This sudden change indicates a deprotonation of the acid. XPS studies revealed the presence of extra oxygen atoms as well as gallium species in the layer, leading to the conclusion that phosphonate and hydrogenophosphonate ions are present in the PPA layer intercalated with H3O+ and Ga3+ ions. This mechanism enables the formation of layers approximately 10 times thicker than those obtained with lower H2O percentages. HREELS indicated that the surface is composed of regions covered by PPA layers and uncovered regions, but the uncovered regions disappeared for water contents equal to or higher than 5%. XPS results are interpreted using a model consisting of a monolayer partially covering the surface and a thick layer. This model is consistent with AFM images revealing roughness on the order of 7 nm for the thick layer and 0.2-0.5 nm for the thin layer. Sonication proves to be an effective method for reducing layer thickness.     

The first spiroconjugated TTF- and TCNQ-type molecules: a new class of electroactive systems?

[Structure: see text] Spiroconjugated TTF-type electron donors (13a-c) and TCNQ-type electron acceptors (10, 11) have been prepared from spiroquinone 9. Cyclic voltammetry reveals a relatively weak accepting ability for 10 and 11, and a strong electron-donor character for 13a-c. Whereas the spiroconjugation introduces a destabilization of the LUMO for compounds 9-11, the opposite is observed for compound 13, thus justifying the redox potential values.     

Structural evolution of phosphated alumina during sol-gel synthesis

Phosphated alumina gels were prepared by the sol-gel method. Gels were aged from 1 to 8 days in air. Gel structure evolution, as time went on, was followed by 27Al magic angle spinning nuclear magnetic resonance, X-ray diffraction, and small-angle X-ray scattering. It is concluded that the aging time is a crucial parameter in the formation of coordinately unsaturated sites of aluminum (AlIV and AlV). The gel network is shown to have a fractal structure.     

On the motion of particles and strings,presymplectic mechanics,and the variational bicomplex

Examples of equations of motion in classical relativistic mechanics are studied: the equations of motion of a charged spinning particle moving in a space-time (with or without torsion) in the presence of an electromagnetic field are derived via Souriau presymplectic reduction. Then, the extension of Souriaus ideas to Lagrangian field theory due to Witten, Crnkovi, Zuckerman is reviewed using the variational bicomplex, the basic properties of the Lund–Regge equations describing the motion of a string interacting with a scalar field and moving in Minkowski spacetime are recalled, and a symplectic structure for their space of solutions is found.This revised version was published online in April 2005. The publishing date was inserted.     

A di-palladium urea complex as a molecular receptor for anions

A new di-nuclear palladium complex containing thiol-urea ligands has been prepared, structurally characterized and its interaction with anionic species studied in solution.     

Effect of rotational energy on the reaction Li + HF(upsilon = 0,j)-->LiF + H: an experimental and computational study

In a crossed molecular-beam study we have measured angular and time-of-flight distributions of the product LiF from the reaction Li + HF(upsilon = 0)-->LiF + H at various collision energies ranging from 97 to 363 meV for three markedly different rotational state distributions of HF obtained at nozzle temperatures close to 315, 510, and 850 K. Particularly, for the low and intermediate collision energies we observe significant effects of the varying j-state populations on the shape of the product angular distributions. At 315 K an additional feature appears in the angular distributions which is interpreted as being due to scattering from HF dimers. The experimental data are compared with simulations of the monomer reaction based on extensive quasiclassical trajectory calculations on a new state-of-the-art ab initio potential energy surface. We find an overall good agreement between the theoretical simulations and the experimental data for the title reaction, especially at the highest HF nozzle temperature.