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.     

Effect of palladium oxide electrode on potentiometric sensor response to carbon monoxide

Ionics - This study aims to explore the potential merits of palladium oxide sensing electrode. PdO is applied on a solid-state potentiometric sensor on an yttria-stabilized zirconia (YSZ)...     

Behavior of cellulose in NaOH/Urea aqueous solution characterized by light scattering and viscometry

Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a ¹³C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10^?2 weight‐average molecular weight (M_w)^0.815 (mL g^?1) in the M_w region from 3.2 × 10⁴ to 12.9 × 10⁴. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were 6.0 nm, 350 nm^?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004     

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).     

A fast modified sine transform for solving block-tridiagonal systems with Toeplitz blocks

In this report we consider block-tridiagonal systems with Toeplitz blocks. Each block is of sizen×n consisting ofn _c×n _c matrices as entries, and there arem×m blocks in the system. The solution of those systems consists of 2n _c m modified sine transforms and an intermediate solution ofn block-tridiagonal systems. Symmetries in the data vectors are exploited such that one modified sine transform can be computed in terms of one Fourier transform of half the length of the original one, hence requiringO(2.5nlog₂ n) operations. Similarly, we only have to solve (n+1)/2 of the intermediate systems due to symmetry.This work was supported by the Swedish National Board for Industrial and Technical Development, NUTEK, under contract No. 89-02539 P.     

Noncooperative facility location games

A noncooperative game theoretical approach is considered for the multifacility location problem. It turns out that the facility location game is a potential game in the sense of Monderer and Shapley and some properties of the game are studied.     

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.