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.     

Mid-IR Range Quantum-Cascade Lasers in Compact Optoacoustic Gas Analyzers

Journal of Applied Spectroscopy - The generation regimes of quantum-cascade lasers for optoacoustic sensors of methane and ammonia are examined, and the tuning and output characteristics of these...     

Impact of thickness of spin-coated P3HT thin films,over their optical and electronic properties

Journal of Solid State Electrochemistry - A study of poly(3-hexylthiophene) (P3HT) thin films by spin-coating process, deposited on conducting glass substrates of fluorine-doped tin oxide (FTO), is...     

Present-Day Practice of Non-Target Chemical Analysis

Journal of Analytical Chemistry - We review the main techniques, procedures, and information products used in non-target analysis (NTA) to reveal the composition of substances. Sampling and sample...     

Chaos break and synchrony enrichment within Hindmarsh–Rose-type memristive neural models

Nonlinear Dynamics - The fluctuation of ions concentration across the cell membrane of neuron can generate a time varying electromagnetic field. Thus, memristors are used to realize the coupling...     

Spectral Properties of Classical Dirac Operators and Operators with Involution in Homogeneous Function Spaces

Differential Equations - We present spectrum localization theorems for Dirac operators and operators with involution in a class of function spaces introduced in [Contemp. Math., 2018, vol. 706, pp....     

Non-crossing monotone paths and binary trees in edge-ordered complete geometric graphs

Acta Mathematica Hungarica - This paper is devoted to the studying of the weak Orlicz–Lorentz space $$\Lambda_X^{\varphi, \infty}(w)$$ , which can be regarded as an extension of weak Orlicz...     

How One can Repair Non-integrable Kahan Discretizations. II. A Planar System with Invariant Curves of Degree 6

Mathematical Physics, Analysis and Geometry - In this paper, we develop the dressing method to study the modified Camassa-Holm equation with the help of reciprocal transformation and the associated...