Aminocatalysis: Beyond Steric Shielding and Hydrogen‐Bonding

The stereochemical outcome of most aminocatalytic transformations is determined by the steric‐shielding or hydrogen‐directing approach. However, in recent years several reactions have appeared in which the stereochemical outcome is beyond these two approaches. This Concept article will highlight such reactions and postulate that the stereochemical outcome can be accounted for by electrostatic interactions between the catalyst‐bound substrate and the reagent in the transition state.     

Mechanistic Insights into the Mode of Action of Bifunctional Pyrrolidine‐Squaramide‐Derived Organocatalysts

The catalytic modes of action of three squaramide‐derived bifunctional organocatalysts have been investigated using DFT methods. The [5+2] cycloaddition between oxidopyrylium ylides and enals was used as the model reaction. Two primary modes were possible for the different catalysts studied. The preference for one mode over the other was due to the possibility of additional favorable π–π interactions between the hydrogen‐bond activated pyrylium ylide and an electron‐deficient aromatic ring bonded to the squaramide NH group. The model can be extended to other reactions catalyzed by the same catalysts, such as formal [2+2] cycloadditions between nitroalkenes and α,β‐unsaturated aldehydes. The computational results were in excellent concurrence with the available experimental reports on the observed total enantioselectivity and differences in diastereoselectivity depending on the substrate and the reaction.     

Donor/Acceptor‐Stabilized 1‐Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction

The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1‐silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1‐silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila‐β‐lactam 3 . Of particular interest, in the presence of 4‐dimethylaminopyridine (DMAP), 1‐silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1‐silaketene complex 8 and cis‐stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four‐membered‐ring intermediate, similar to that proposed by Chauvin and co‐workers for the transition‐metal‐based olefin metathesis.     

High pressure effect on structural and spectroscopic properties of Sm3+-doped alkali silicate glasses

Structural and spectroscopic properties of Sm³⁺-doped alkali silicate glasses were investigated after densification at 7.7?GPa in a large volume high pressure apparatus. The glass composition was 33M₂O?+?66SiO₂?+?1Sm₂O₃, where M?=?Li, Na or K. Raman and infrared spectroscopy revealed small changes in the vibrational modes dependent on the alkali ion. Irreversible changes were observed in the optical absorption spectra of Sm³⁺ ions. The Judd–Ofelt parameters were calculated to evaluate the effect of pressure on the local field. For lithium silicate, Ω₂ parameter increased, suggesting the densification increased the local asymmetry of the Sm³⁺ environment. For sodium silicate, this parameter decreased considerably, suggesting the opposite effect on the local field, while for potassium silicate, it remained practically unchanged. The changes induced by high pressure are probably due to the irreversible changes in the distances and bond angles between the rare earth ion and the ligands.     

Evidence of a Mixed Magnetic Phase in EuMgGe: A Semi­metallic Zintl Compound with TiNiSi Structure Type

The ternary Zintl phase EuMgGe was synthesized from the elements, and its structure solved by single‐crystal X‐ray diffraction. Chemical bonding is discussed, by means of electronic structure calculations at the DFT level and its physical properties characterized with respect to electronic conductivity, magnetic susceptibility, specific heat capacity, and magnetoresistivity. The compound may be interpreted according to the Zintl‐Klemm concept as (Eu²⁺)(Mg²⁺)(Ge^4–) with isolated germanium anions. Resistivity measurements reveal a semimetallic character, which is consistent with the vanishing energy gap obtained from our calculations. The magnetic susceptibility and the specific heat indicate that two consecutive transitions take place, at 9 and 16 K, and they show evidence of magnetic frustration. A possible physical scenario for this magnetic behavior is discussed based on known models of partially frustrated magnets.     

Insights into the Antimicrobial Activity of Hydrated Cobaltmolybdate Doped with Copper

Molybdates are biocidal materials that can be useful in coating surfaces that are susceptible to contamination and the spread of microorganisms. The aim of this work was to investigate the effects of copper doping of hydrated cobalt molybdate, synthesized by the co-precipitation method, on its antibacterial activity and to elucidate the structural and morphological changes caused by the dopant in the material. The synthesized materials were characterized by PXRD, Fourier Transformed Infrared (FTIR), thermogravimetric analysis/differential scanning calorimetry (TG/DSC), and SEM-Energy Dispersive Spectroscopy (SEM-EDS). The antibacterial response of the materials was verified using the Minimum Inhibitory Concentration (MIC) employing the broth microdilution method. The size of the CoMoO₄·1.03H₂O microparticles gradually increased as the percentage of copper increased, decreasing the energy that is needed to promote the transition from the hydrated to the beta phase and changing the color of material. CoMoO₄·1.03H₂O obtained better bactericidal performance against the tested strains of Staphylococcus aureus (gram-positive) than Escherichia coli (gram-negative). However, an interesting point was that the use of copper as a doping agent for hydrated cobalt molybdate caused an increase of MIC value in the presence of E. coli and S. aureus strains. The study demonstrates the need for caution in the use of copper as a doping material in biocidal matrices, such as cobalt molybdate.