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 hyperbolic three-phase flow model

We introduce a hyperbolic entropy-consistent model to describe three-phase flows, which ensures that void fractions, mass fractions and pressures remain positive through single waves occurring in the one dimensional solution of the Riemann problem. To cite this article: J.-M. Hérard, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Coupled perpendicular magnetization in Fe/Cu/Fe trilayers

Ultrathin epitaxial Fe films on Cu(1 0 0) with perpendicular magnetization have been used as templates for the preparation of FCC Fe/Cu/Fe trilayers. The magnetic anisotropy and the coupling of these films have been studied by in-situ magneto optical Kerr effect measurements and Kerr microscopy. The magnetic coupling of both Fe layers is found to be dominated by magnetostatic interaction. Adsorbate-induced spin reorientation in the top layer also causes spin reorientation in the bottom layer. The governing role of the Fe-vacuum interface for the magnetism of the whole trilayer is demonstrated.     

Stereoselective synthesis of trifluoromethyl-substituted 1,2-diamines by aza-Michael reaction with trans-3,3,3-trifluoro-1-nitropropene

Aza-Michael addition of optically pure 4-phenyl-2-oxazolidinone to 3,3,3-trifluoro-1-nitropropene proceeds smoothly at low temperature with a high yield. Diastereoselectivity of the addition depends on the base used and lithiated species proved to be highly efficient affording 92% de. Optically pure 1,2-diamino-3,3,3-trifluoropropane is prepared in 58% yield from the aza-Michael addition product through a three-step procedure.     

The measurement of beta asymmetries at UNISOR/NOF using external plastic scintillator detectors

The performance of two external plastic scintillator detectors has been tested in an off-line mode using a source of¹⁰⁶RuFe at UNISOR/NOF. The measurement of beta asymmetries at various temperatures has resulted in the reproduction of the previously-determined magnetic dipole moment for the 1⁺ ground state of¹⁰⁶Rh and in addition the conclusion that the sign of this moment is positive.     

Closure laws for a two-fluid two-pressure modelLois de fermeture pour un modèle à deux pressions d'écoulement diphasique

Closure laws for interfacial pressure and interfacial velocity are proposed within the frame work of two-pressure two-phase flow models. These enable us to ensure positivity of void fractions, mass fractions and internal energies when investigating field by field waves in the Riemann problem. To cite this article: F. Coquel et al., C. R. Acad. Sci. Paris, Ser. I 334 (2002) 927–932.     

The Shapley value for cooperative games under precedence constraints

Cooperative games are considered where only those coalitions of players are feasible that respect a given precedence structure on the set of players. Strengthening the classical symmetry axiom, we obtain three axioms that give rise to a unique Shapley value in this model. The Shapley value is seen to reflect the expected marginal contribution of a player to a feasible random coalition, which allows us to evaluate the Shapley value nondeterministically. We show that every exact algorithm for the Shapley value requires an exponential number of operations already in the classical case and that even restriction to simple games is #P-hard in general. Furthermore, we outline how the multi-choice cooperative games of Hsiao and Raghavan can be treated in our context, which leads to a Shapley value that does not depend on pre-assigned weights. Finally, the relationship between the Shapley value and the permission value of Gilles, Owen and van den Brink is discussed. Both refer to formally similar models of cooperative games but reflect complementary interpretations of the precedence constraints and thus give rise to fundamentally different solution concepts.     

Ethyl-4,4,4-trifluoroacetoacetate (ETFAA), a powerful building block for enantiopure chirons in trifluoromethyl-β-amino acid series

Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure.