Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

On-line Method for Montelukast Determination in Bile Salt Medium with Multivariate Optimization and Fluorescent Detection

Journal of Analytical Chemistry - The present development involved a flow injection strategy using a mini-column of multiwalled carbon nanotubes and fluorescent detection (λex of 283 nm,...     

A type III porous-thermo-elastic problem with quasi-static microvoids

Meccanica - In this work we study, from the numerical point of view, a one-dimensional thermoelastic problem where the thermal law is of type III. Quasi-static microvoids are also assumed within...     

Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

ELECTRONIC STRUCTURE AND CHEMICAL BOND IN 9,9,10,10-TETRAETHYNYL-9,10- DIHYDRODISILAANTHRACENE

Journal of Structural Chemistry - Atomic and electronic structures of cyclic organosilicon compound 9,9,10,10-tetraethynyl-9,10-dihydrodisilaanthracene are studied by the density functional theory....     

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...     

Thermodynamic and Electrochemical Investigations of Potassium–Antimony Alloys

Russian Journal of Applied Chemistry - In September 1975, the head of Russian electrochemists, Academician A.N. Frumkin (1895–1976), in his report at the XI Mendeleev Congress on General and...     

Evolutionary Development and Structural Diversity of Natural Antimicrobial Peptides,Peptidometics, and Cationic Amphiphiles Based on Amino Acids

Russian Journal of General Chemistry - The review article traces the main trends of the synthetic approach to the solution of the problem of overcoming the resistance of pathogenic bacterial...     

On the Possibility of the Effective Isotope-Selective Infrared Dissociation of 235UF6 Molecules Vibrationally Excited by Bichromatic Laser Radiation

JETP Letters - Using the spectroscopic data on the 235UF6 and 238UF6 molecules and on the lasing frequencies of CF4 and para-H2 lasers and recent results, a method has been proposed to increase the...     

Magnetic Properties of FeBO3 in the Low-Spin State

JETP Letters - Changes in the magnetic properties of FeBO3 single crystals in the course of spin crossover occurring with increasing pressure up to 63 GPa are studied both experimentally and...