Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

A Stochastic Subgradient Method for Distributionally Robust Non-convex and Non-smooth Learning

Journal of Optimization Theory and Applications - We consider a distributionally robust formulation of stochastic optimization problems arising in statistical learning, where robustness is with...     

Dichlorocarbene and analogs: discovery,properties and reactions

Russian Chemical Bulletin - The discovery and studies of chemistry of dichlorocarbene and other electron deficient carbenes are discussed.     

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.     

Synthesis and Properties of Azoles and Their Derivatives. Part 70. Nitroallylic Systems in [2 + 3] Cycloaddition Reactions with Nitrones: A DFT Computational Study

The analysis of electrophilicity indexes and the results of potential energy surface (PES) simulations for the reaction pathways proved that the [2 + 3] cycloadditions of nitroallylic systems with nitrones should be considered nonpolar reactions. Our simulations proved that the reactions always proceed via a one‐step mechanism through a prereaction complex. Although the symmetry of respective transition states is quite varied, their polarity is low and does not change when a polar medium is introduced to the reaction environment. When the polarity of the reaction medium increases, the kinetic pathway preference does not change. The regiochemistry of the cycloadditions tested may, however, be controlled to some extent by steric effects.     

Space-Time Directional Lyapunov Exponents for Cellular Automata

Space-time directional Lyapunov exponents are introduced. They describe the maximal velocity of propagation to the right or to the left of fronts of perturbations in a frame moving with a given velocity. The continuity of these exponents as function of the velocity and an inequality relating them to the directional entropy is proved.