Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Logarithmic temperature dependence of the conductivity of the two-dimensional metal

We report on the first observation and studies of a weak delocalizing logarithmic temperature dependence of the conductivity, which causes the conductivity of the 2D metal to increase as T decreases down to 16 mK. The prefactor of the logarithmic dependence is found to decrease gradually with density, to vanish at a critical density n _c , 2∼2×10¹² cm⁻², and then to have the opposite sign at n>n _c ,2. The second critical density sets the upper limit on the existence region of the 2D metal, whereas the conductivity at the critical point, G _c ,2∼120e ²/h, sets an upper (low-temperature) limit on its conductivity. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 6, 497–501 (25 September 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Influence functions and efficiencies of the canonical correlation and vector estimates based on scatter and shape matrices

In this paper, the influence functions and limiting distributions of the canonical correlations and coefficients based on affine equivariant scatter matrices are developed for elliptically symmetric distributions. General formulas for limiting variances and covariances of the canonical correlations and canonical vectors based on scatter matrices are obtained. Also the use of the so-called shape matrices in canonical analysis is investigated. The scatter and shape matrices based on the affine equivariant Sign Covariance Matrix as well as the Tyler's shape matrix serve as examples. Their finite sample and limiting efficiencies are compared to those of the Minimum Covariance Determinant estimators and S-estimator through theoretical and simulation studies. The theory is illustrated by an example.     

Fundamental groups of the complements of certain plane non-tame torus sextics

The moduli space of torus sextics with the configuration of singularities {A₂+A₅+2E₆} has two connected components. We compute the fundamental groups π₁(CP²−C) for sextics C in both components and study their differences.     

Carbon precipitation and diffusion in SiGeC alloys under silicon self-interstitial injection

In this work we investigate the diffusion and precipitation of supersaturated substitutional carbon in 200-nm-thick SiGeC layers buried under a silicon cap layer of 40 nm. The samples were annealed in either inert (N₂) or oxidizing (O₂) ambient at 850 °C for times ranging from 2 to 10 h. The silicon self-interstitial (I) flux coming from the surface under oxidation enhances the C diffusion with respect to the N₂-annealed samples. In the early stages of the oxidation process, the loss of C from the SiGeC layer by diffusion across the layer/cap interface dominates. This phenomenon saturates after an initial period (2–4 h), which depends on the C concentration. This saturation is due to the formation and growth of C-containing precipitates that are promoted by the I injection and act as a sink for mobile C atoms. The influence of carbon concentration on the competition between precipitation and diffusion is discussed. Received: 19 October 2001 / Accepted: 19 December 2001 / Published online: 20 March 2002 / Published online: 20 March 2002     

Automorphismes des courbes modulaires X(n) en caractéristique p

 We prove that the group of automorphisms of the modular curve prime, in characteristic when the curve is ordinary is always when and a simple group when p = 2 or 3. In the non-ordinary cases we give informations about the ramification of and describe when q = 7,11 and 13 for all . Received: 12 October 2001 / Revised version: 29 April 2002     

On the non existence of monotone linear schema for some linear parabolic equations

In this Note, we present a result concerning the non existence of linear monotone schema with fixed stencil on regular meshes for some linear parabolic equation in two dimensions. The parabolic equations of interest arise from non isotropic diffusion modelling. A corollary is that no linear monotone 9 points-schemes can be designed for the one-dimensional heat equation emerged in the plane with an arbitrary direction of diffusion. Some applications of this result are provided: for the Fokker–Planck–Lorentz model for electrons in the context of plasma physics; all linear monotone scheme for the one-dimensional hyperbolic heat equation treated as a two-dimensional problem are not consistent in the diffusion limit for an arbitrary direction of propagation. We also examine the case of the Landau equation. To cite this article: C. Buet, S. Cordier, C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

Optimal mappings with minimum number of connected components in tree-to-tree comparison problems

In this paper we consider the problem of finding a minimum cost mapping between two unordered trees which induces a graph with a minimum number of connected components. The proposed algorithm is based on the generalization of an algorithm for computing an edit distance between trees, and it solves the stated problem in sequential time precisely in O(|T₁|×|T₂|×(degT₁+degT₂)×log₂(degT₁+degT₂)).     

Amplitude des oscillations d'ondes solitaires généralisées

Various physical systems of dispersive waves admit solutions in the form of generalized solitary waves. Such waves result from the resonance between a long localized wave and short periodic oscillations. Many estimates (rigorous and numerical) have been given for the amplitude of the ripples in the tail of the generalized solitary wave when its central part has a sech² shape. This Note provides estimates (not yet rigorous) for the ripple amplitude when the central part is flat and wide. To cite this article: C. Fochesato, F. Dias, C. R. Acad. Sci. Paris, Ser. I 337 (2003).