Nitrenium Salts in Lewis Acid Catalysis

Molecular compounds featuring nitrogen atoms are typically regarded as Lewis bases and are extensively employed as donor ligands in coordination chemistry or as nucleophiles in organic chemistry. By contrast, electrophilic nitrogen‐containing compounds are much rarer. Nitrenium cations are a new family of nitrogen‐based Lewis acids, the reactivity of which remains largely unexplored. In this work, nitrenium ions are explored as catalysts in five organic transformations. These reactions are the first examples of Lewis acid catalysis employing nitrogen as the site of substrate activation. Moreover, these compounds are readily accessed from commercially available reagents and exhibit remarkable stability toward moisture, allowing for benchtop transformations without the need to pretreat solvents.     

The effects of grain shape and frustration in a granular column near jamming

We investigate the full phase diagram of a column of grains near jamming, as a function of varying levels of frustration. Frustration is modelled by the effect of two opposing fields on a grain, due respectively to grains above and below it. The resulting four dynamical regimes (ballistic, logarithmic, activated and glassy) are characterised by means of the jamming time of zero-temperature dynamics, and of the statistics of attractors reached by the latter. Shape effects are most pronounced in the cases of strong and weak frustration, and essentially disappear around a mean-field point.     

The nature of marbled Terra Sigillata slips: a combined μXRF and μXRD investigation

In addition to the red terra sigillata production, the largest Gallic workshop (La Graufesenque) made a special type of terra sigillata, called “marbled” by the archaeologists. Produced exclusively at this site, this pottery is characterized by a surface finish made of a mixture of yellow and red slips. Because the two slips are intimately mixed, it is difficult to obtain the precise composition of one of the two constituents without contamination from the other. In order to obtain very precise correlation at the appropriate scale between the color aspect and the elemental and mineralogical phase distributions in the slip, combined electron microprobe, X-ray micro spectroscopies and micro diffraction on cross-sectional samples were performed. The aim of this study is to discover how potters were able to produce this unique type of terra sigillata and especially this particular slip of an intense yellow color. Results show that the yellow component of marbled sigillata was made from a titanium-rich clay preparation. The color is due to the formation of a pseudobrookite (TiFe₂O₅) phase in the yellow part of the slip, the main characteristics of that structure being considered nowadays as essential for the fabrication of stable yellow ceramic pigments. Its physical properties such as high refractive indices and a melting point higher than that of most silicates widely used as ceramic colorants are indeed determinant for this kind of application. Finally, the red parts have a similar composition (elementary and mineralogical) to the one of standard red slip.     

Hybrid systems through natural product leads: an approach towards new molecular entities

Hybrid systems are constructs of different molecular entities, natural or unnatural, to generate functional molecules in which the characteristics of various components are modulated, amplified or give rise to entirely new properties. These hybrids can be designed from carefully selected components either through domain integration of key structural/functional features or via straightforward covalent linkages. Some of the recently reported hybrid systems based on steroid, carbohydrate, C60-fullerene platforms, amongst others, mainly crafted with the object of enhancement of the therapeutical spectrum, will be discussed.     

Electrophilic additions to a 2-methylenebicyclo[2.1.1]hexane system: probing pi-face selectivity for electrostatic and orbital effects

[reaction: see text] 5-exo-Bicyclo[2.1.1]hexane derivatives with remote electron-withdrawing substituents exhibit very modest face selectivity during electrophilic additions due to interplay of several electronic factors. These experimental results have been probed through ab initio MESP maps, bond density calculations, and energetics involved in pre-reaction complexation.     

Singularity in the thermal boundary resistance between superfluid (4)He and a solid surface

We report new measurements in four cells of the thermal boundary resistance R between copper and (4)He below but near the superfluid-transition temperature T(lambda). For 10(-7)< or =t identical to 1-T/T(lambda))< or =10(-4) fits of R = R(0)t(-x(b))+R(B) to the data yielded x(b) approximately equal to 0.18, whereas a fit to theoretical values based on the renormalization-group theory yielded x(b) = 0.23. Alternatively, a good fit of the theory to the data could be obtained if the amplitude of the prediction was reduced by a factor close to 2. The results raise the question whether the boundary conditions used in the theory should be modified.     

The problem of the relation between double pomeron exchange in inclusive and exclusive experiments

The pionization region of the inclusive single-particle spectrum is accounted for by double pomeron exchange in the absorptive part of a six-point amplitude. In this paper a multiperipheral model for the six-point amplitude with double pomeron exchange is used for continuation by crossing and analyticity to the physical region of the exclusive two particle → four particle production process. The cross section for π^? p → π^?(π⁺π^?)p in the double-Regge region is then calculated and compared with the experimental analysis of Lipes, Zweig and Robertson which sets an upper bound to the strength of the double pomeron exchange coupling. This upper bound, coupled with the model for continuation to the inclusive cross section, is shown to give too small a magnitude for the double pomeron exchange in the pionization region. Further avenues for investigation are discussed.     

Cubyl-caged systems: regiochemical steering of cationic rearrangements by distal groups

Novel carbonium ion rearrangements of substituted 1,3-bishomocubanones $\text{3}$ & $\text{4}$ to tricyclo(4.2.0.0^3,8)octane and bicyclo(3.2.1)octane ring systems are reported.     

On the fluxional behaviour of a polycyclic (4.4.2) propella-2,4-diene

Existence of bicyclo (4.2.0) octa-2,4-diene ? 1,3,5-cyclooctatriene type of valence isomerisation in a polycyclic propellane framework has been demonstrated through cycloaddition and thermolysis reactions.