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.     

Transverse Thermomagnetic Effect in the Two-Dimensional Electron Gas of Surface Semiconductor Superlattice

Journal of Experimental and Theoretical Physics - The surface current density of charge carriers in two-dimensional doubly periodic n-type semiconductor superlattices in an external magnetic field...     

Synthesis and Properties of Magnetically Susceptible Porous Carbon Materials Based on Hydrolysis Lignin Modified with ZnCl2 and FeCl3

Russian Journal of Applied Chemistry - A method for the disposal of hydrolysis lignin waste based on its modification with ZnCl2 and FeCl3 and subsequent carbonization at 800°C was proposed....     

Determination of Vardenafil in Pure and Dosage Forms by Spectrophotometry

Journal of Applied Spectroscopy - Three simple, sensitive, precise, and rapid spectrophotometric methods are developed and optimized for the assay of vardenafil in pharmaceutical formulations. The...     

On lower iteration complexity bounds for the convex concave saddle point problems

Mathematical Programming - In this paper, we study the lower iteration complexity bounds for finding the saddle point of a strongly convex and strongly concave saddle point problem: $$\min _x\max...     

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...     

Excellent UV-absorbing cotton fabric with high durability and hydrophobicity based on surface-initiated ATRP of polymerizable organic UV-absorber

Cellulose - Ultraviolet (UV) protective cotton fabric is a convenient and reliable way to protect human body from sunlight. Herein, a polymerizable UV-absorber,...     

Thermoheliox: effect on the functional hemodynamics of the human brain

A kinetic study of the effect of thermoheliox (inhalation of a helium and oxygen mixture, 70 °C) on the functional hemodynamics of the human brain by functional magnetic resonance imaging was carried out. The dynamic responses of the BOLD signal were found to be biphasic. An empirical equation describing the first phase of the hemodynamic response to visual stimulus was proposed. It was shown that preliminary inhalation of thermoheliox stimulates the hemodynamic responses by slowing down the vasoconstriction.