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.     

A finite difference method for the static limit analysis of masonry domes under seismic loads

Meccanica - The static limit analysis of axially symmetric masonry domes subject to pseudo-static seismic forces is addressed. The stress state in the dome is represented by the shell stress...     

(O-Si)-Chelate acetic and benzoic acid N-(fluorosilylmethyl)amides: synthesis and structure

Russian Chemical Bulletin - New representatives of (O-Si)-chelate compounds, N-(fluorosilyl)methyl derivatives of N-methylacetamide, N-methylbenzamide, N-phenylacetamide, and N-phenylbenzamide,...     

Chitosan-Based Magnetic Polymetallic Pd-Catalysts for Heck Reaction in Aqueous Media

Russian Journal of General Chemistry - A mechanochemical method was developed for the synthesis of ferromagnetic Pd–Fe–Co–Ni composites based on the natural biopolymer chitosan,...     

Equivalent cyclic polygon of a euclidean travelling salesman problem tour and modified formulation

Central European Journal of Operations Research - We define a geometric transformation of Euclidean Travelling Salesman Problem (TSP) tours that leads to a new formulation of the TSP. For every...     

Finite-Time Stabilization of Differential Systems with Incommensurable Delays

Differential Equations - For a spectrally controllable linear autonomous system with incommensurable delays, we construct a dynamic state feedback in the form of a differential-difference...     

On a new class of dynamic Hardy-type inequalities and some related generalizations

Aequationes mathematicae - In this paper, we establish a new class of dynamic inequalities of Hardy’s type which generalize and improve some recent results given in the literature. More...     

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....     

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...