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,...     

(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,...     

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 the Problem of Separation of Variables in Systems of Ordinary Differential Equations

Differential Equations - Conditions for the separation of variables in autonomous systems of general differential equations are discussed. The approach is based on Liouville’s idea of...     

Epoxy Nanocomposites with Metal-Containing Fillers: Synthesis,Structure, and Properties

Russian Journal of Applied Chemistry - Recent achievements in the field of the development of preparation methods and study of structure and properties of epoxy nanocomposites with metal-containing...     

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...     

Cosmological constant,scalar field,and the coincidence problem

Theoretical and Mathematical Physics - We study a phenomenological model in which dark matter in the cosmological constant form is identified with the mean energy–momentum tensor of a...