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.     

How deeply are core electrons perturbed when valence electrons are spin polarized? The case study of transition metal compounds

The ferromagnetic and antiferromagnetic wave functions of the KMnF₃ perovskite have been evaluated quantum-mechanically by using an all electron approach and, for comparison, pseudopotentials on the transition metal and the fluorine ions. It is shown that the different number of α and β electrons in the d shell of Mn perturbs the inner shells, with shifts between the α and β eigenvalues that can be as large as 6 eV for the 3s level, and is far from negligible also for the 2s and 2p states. The valence electrons of F are polarized by the majority spin electrons of Mn, and in turn, spin polarize their 1s electrons. When a pseudopotential is used, such a spin polarization of the core functions of Mn and F can obviously not take place. The importance of such a spin polarization can be appreciated by comparing (i) the spin density at the Mn and F nuclear position, and then the Fermi contact constant, a crucial quantity for the hyperfine coupling, and (ii) the ferromagnetic–antiferromagnetic energy difference, when obtained with an all electron or a pseudopotential scheme, and exploring how the latter varies with pressure. This difference is as large as 50% of the all electron datum, and is mainly due to the rigid treatment of the F ion core. The effect of five different functionals on the core spin polarization is documented.     

DNS of premixed turbulent V-flame: coupling spectral and finite difference methods

To allow for a reliable examination of the interaction between velocity fluctuations, acoustics and combustion, a novel numerical procedure is discussed in which a spectral solution of the Navier–Stokes equations is directly associated to a high-order finite difference fully compressible DNS solver (sixth order PADE). Using this combination of high-order solvers with accurate boundary conditions, simulations have been performed where a turbulent premixed V-shape flame develops in grid turbulence. In the light of the DNS results, a sub-model for premixed turbulent combustion is analyzed. To cite this article: R. Hauguel et al., C. R. Mecanique 333 (2005).     

Transcranial direct current stimulation of the prefrontal cortex modulates working memory performance: combined behavioural and electrophysiological evidence

Background  

Transcranial direct current stimulation (tDCS) is a technique that can systematically modify behaviour by inducing changes in the underlying brain function. In order to better understand the neuromodulatory effect of tDCS, the present study examined the impact of tDCS on performance in a working memory (WM) task and its underlying neural activity. In two experimental sessions, participants performed a letter two-back WM task after sham and either anodal or cathodal tDCS over the left dorsolateral prefrontal cortex (DLPFC).     

Thiazonaphthalimide derivatives: Synthesis and interaction with DNA

The synthesis of several thiazonaphthalimide derivatives is described. The exclusive formation of angular rather than linear isomers was unequivocally demonstrated by NMR and single crystal X-ray diffraction. Their photophysical properties and ability to bind calf-Thymus DNA with affinities in the range of 10⁴ makes them interesting candidates to probe DNA by fluorescence.     

A Convenient Synthesis of Diversely Substituted N,N-Dimethyl-4-oxo-2-(E)-alkenamides

An efficient synthesis of diversely substituted N,N-dimethyl-4-oxo-2-(E)-alkenamides is reported. These derivatives were obtained in three steps from I,4benzodioxin with fair to good yields