Catalytic Asymmetric Syntheses of Alkylidenecyclopropanes from Allenoates with Donor-Acceptor and Diacceptor Diazo Reagents

The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh₂((S)-TCPTAD)₄ or Rh₂((R)-BTPCP)₄ catalysts (up to 95 % yield, >95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular C−H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r.     

Analysis of a tripartite entanglement distribution switch

Queueing Systems - We study a quantum switch that distributes tripartite entangled states to sets of users. The entanglement switching process requires two steps: First, each user attempts to...     

Auger electron emission in proton-induced interactions in living matter: A TILDA-V Monte Carlo tracking

The present work focuses on studying the contribution of the Auger electron emission in proton-induced interactions in biological matter. The Monte Carlo track-structure code, TILDA-V, was then used for modeling the protons beams of 10 keV to 100 MeV in biological matter, namely, water vapor and hydrated DNA. The main ionizing processes are described by means of an extensive set of ab initio differential and total cross sections computed within a quantum-mechanical CDW-EIS approximation.     

Measuring fluorescence to track a quantum emitter's state: a theory review

We review the continuous monitoring of a qubit through its spontaneous emission, at an introductory level. Contemporary experiments have been able to collect the fluorescence of an artificial atom in a cavity and transmission line, and then make measurements of that emission to obtain diffusive quantum trajectories in the qubit's state. We give a straightforward theoretical overview of such scenarios, using a framework based on Kraus operators derived from a Bayesian update concept; we apply this flexible framework across common types of measurements including photodetection, homodyne, and heterodyne monitoring and illustrate its equivalence to the stochastic master equation formalism throughout. Special emphasis is given to homodyne (phase-sensitive) monitoring of fluorescence. The examples we develop are used to illustrate basic methods in quantum trajectories, but also to introduce some more advanced topics of contemporary interest, including the arrow of time in quantum measurement, and trajectories following optimal measurement records derived from a variational principle. The derivations we perform lead directly from the development of a simple model to an understanding of recent experimental results.     

Unusual Bonding and Properties in Main Group Element Chemistry: Rational Synthesis,Characterization, and Experimental Electron Density Determination of Mixed‐Valent Tetraphosphetes

Five dispirocyclic λ³,λ⁵‐tetraphosphetes [{R₂Si(NR¹)(NR²)P₂}₂] (R¹ = R² and R¹ ≠ R²) are easily prepared in almost quantitative yields via photolysis of the respective bis(trimethylsilyl)phosphanyldiazaphosphasiletidines with intense visible light. These deep‐yellow low‐coordinate phosphorus compounds can be considered as the first higher congeners of the well‐known cyclodiphosphazenes. The tetraphosphetes are remarkably stable in air and show unexpected molecular properties related to the unique bonding situation of the central four‐π‐electron four‐membered phosphorus ring. The extent of rhombic distortion of the central P₄ ring is remarkable due to an unusually acute angle at the σ²‐phosphorus atoms. All of the P?P bonds are approximately equal in length. The distances are in the middle of the range given by phosphorus single and double bonds. The anisotropic absorption of visible light that can easily be observed in the case of the yellow/colorless dichroic crystals of [{Me₂Si(NtBu)(NtBu)P₂}₂] and the exceptional ³¹P NMR chemical shift of the σ²‐phosphorus atoms are the most remarkable features of the λ³,λ⁵‐tetraphosphetes. In the case of [{Me₂Si(NtBu)(NtBu)P₂}₂], the Hansen–Coppens multipole model is applied to extract the electron density from high‐resolution X‐ray diffraction data obtained at 100 K. Static deformation density and topological analysis reveal a unique bonding situation in the central unsaturated P₄ fragment characterized by polar σ‐bonding, pronounced out‐of‐ring non‐bonding lone pair density on the σ²‐phosphorus atoms, and an additional non‐classical three‐center back‐bonding contribution.     

“(Diphosphine)Nickel”‐Catalyzed Negishi Cross‐Coupling: An Experimental and Theoretical Study

The use of a strongly donating “(bis‐dialkylphosphine)Ni” fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni⁰/Ni^II cycle is operative in this system.     

An analysis of over-relaxation in a kinetic approximation of systems of conservation laws

The over-relaxation approach is an alternative to the Jin–Xin relaxation method in order to apply the equilibrium source term in a more precise way. This is also a key ingredient of the lattice Boltzmann method for achieving second-order accuracy. In this work, we provide an analysis of the over-relaxation kinetic scheme. We compute its equivalent equation, which is particularly useful for devising stable boundary conditions for the hidden kinetic variables.     

A Switch in the Hydrophobic/Hydrophilic Gas-Adsorption Character of Prussian Blue Analogues: An Affinity Control for Smart Gas Sorption

Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.