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.     

Thermal,morphostructural and spectrometric characterization of an antibacterial kaolinite-based filter modified with silver for water treatment

Journal of Thermal Analysis and Calorimetry - The aim of this work is to synthesize and characterize a new structured silver–clay dried, calcined or sintered at different temperatures...     

Growth rate of the Schrödinger group on Zhidkov spaces

We give an upper bound on the growth rate of the Schrödinger group on Zhidkov spaces. In dimension 1, we prove that this bound is sharp. To cite this article: C. Gallo, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Exact Max-SAT solvers for over-constrained problems

We present a new generic problem solving approach for over-constrained problems based on Max-SAT. We first define a Boolean clausal form formalism, called soft CNF formulas, that deals with blocks of clauses instead of individual clauses, and that allows one to declare each block either as hard (i.e., must be satisfied by any solution) or soft (i.e., can be violated by some solution). We then present two Max-SAT solvers that find a truth assignment that satisfies all the hard blocks of clauses and the maximum number of soft blocks of clauses. Our solvers are branch and bound algorithms equipped with original lazy data structures, powerful inference techniques, good quality lower bounds, and original variable selection heuristics. Finally, we report an experimental investigation on a representative sample of instances (random 2-SAT, Max-CSP, graph coloring, pigeon hole and quasigroup completion) which provides experimental evidence that our approach is very competitive compared with the state-of-the-art approaches developed in the CSP and SAT communities. Research partially supported by projects TIN2004-07933-C03-03 and TIC2003-00950 funded by the Ministerio de Educación y Ciencia. The second author is supported by a grant Ramón y Cajal.     

Mathematical and numerical analysis of a simplified time-dependent viscoelastic flow

A time-dependent model corresponding to an Oldroyd-B viscoelastic fluid is considered, the convective terms being disregarded. Global existence in time is proved in Banach spaces provided the data are small enough, using the implicit function theorem and a maximum regularity property for a three fields Stokes problem. A finite element discretization in space is then proposed. Existence of the numerical solution is proved for small data, so as a priori error estimates, using again an implicit function theorem. Supported by the Swiss National Science Foundation. Fellowship PBEL2–114311.     

Synthesis and thermal crosslinking of oxazolidine‐functionalized polyurethanes

A new oxazolidine derivative was obtained from phenol, 2‐amino‐2‐methylpropane‐1,3‐diol and paraformaldehyde. The reaction of this novel oxazolidine diol with phenylisocyanate lead to a urethane model compound which can be polymerized thermally by oxazolidine ring opening to give a Mannich bridge structure. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (M_w ～ 400) with 4,4′‐methylenbis (cyclohexylisocyanate) (HMDI, 90% isomers mixture). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials which showed improved thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4965–4973, 2007