C-F and C-H bond activation of fluorobenzenes and fluoropyridines at transition metal centers: how fluorine tips the scales

In this Account, we describe the transition metal-mediated cleavage of C-F and C-H bonds in fluoroaromatic and fluoroheteroaromatic molecules. The simplest reactions of perfluoroarenes result in C-F oxida tive addition, but C-H activation competes with C-F activation for partially fluorinated molecules. We first consider the reactivity of the fluoroaromatics toward nickel and platinum complexes, but extend to rhenium and rhodium where they give special insight. Sections on spectroscopy and molecular structure are followed by discussions of energetics and mechanism that incorporate experimental and computational results. We highlight special characteristics of the metal-fluorine bond and the influence of the fluorine substituents on energetics and mechanism. Fluoroaromatics reacting at an ML(2) center initially yield η(2)-arene complexes, followed usually by oxidative addition to generate MF(Ar(F))(L)(2) or MH(Ar(F))(L)(2) (M is Ni, Pd, or Pt; L is trialkylphosphine). The outcome of competition between C-F and C-H bond activation is strongly metal dependent and regioselective. When C-H bonds of fluoroaromatics are activated, there is a preference for the remaining C-F bonds to lie ortho to the metal. An unusual feature of metal-fluorine bonds is their response to replacement of nickel by platinum. The Pt-F bonds are weaker than their nickel counterparts; the opposite is true for M-H bonds. Metal-fluorine bonds are sufficiently polar to form M-F···H-X hydrogen bonds and M-F···I-C(6)F(5) halogen bonds. In the competition between C-F and C-H activation, the thermodynamic product is always the metal fluoride, but marked differences emerge between metals in the energetics of C-H activation. In metal-fluoroaryl bonds, ortho-fluorine substituents generally control regioselectivity and make C-H activation more energetically favorable. The role of fluorine substituents in directing C-H activation is traced to their effect on bond energies. Correlations between M-C and H-C bond energies demonstrate that M-C bond energies increase far more on ortho-fluorine substitution than do H-C bonds. Conventional oxidative addition reactions involve a three-center triangular transition state between the carbon, metal, and X, where X is hydrogen or fluorine, but M(d)-F(2p) repulsion raises the activation energies when X is fluorine. Platinum complexes exhibit an alternative set of reactions involving rearrangement of the phosphine and the fluoroaromatics to a metal(alkyl)(fluorophosphine), M(R)(Ar(F))(PR(3))(PR(2)F). In these phosphine-assisted C-F activation reactions, the phosphine is no spectator but rather is intimately involved as a fluorine acceptor. Addition of the C-F bond across the M-PR(3) bond leads to a metallophosphorane four-center transition state; subsequent transfer of the R group to the metal generates the fluorophosphine product. We find evidence that a phosphine-assisted pathway may even be significant in some apparently simple oxidative addition reactions. While transition metal catalysis has revolutionized hydrocarbon chemistry, its impact on fluorocarbon chemistry has been more limited. Recent developments have changed the outlook as catalytic reactions involving C-F or C-H bond activation of fluorocarbons have emerged. The principles established here have several implications for catalysis, including the regioselectivity of C-H activation and the unfavorable energetics of C-F reductive elimination. Palladium-catalyzed C-H arylation is analyzed to illustrate how ortho-fluorine substituents influence thermodynamics, kinetics, and regioselectivity.     

A Highly Active and Selective Manganese Oxide Promoted Cobalt-on-Silica Fischer�CTropsch Catalyst

A highly active and selective manganese oxide-promoted silica-supported cobalt catalyst for the Fischer?CTropsch reaction is reported. Co/MnO/SiO₂ catalysts were prepared via impregnation of a cobalt nitrate and manganese nitrate precursor, followed by drying and calcination in an NO/He flow. The catalysts were studied with STEM?CEELS, infrared spectroscopy measurements of adsorbed CO and Steady-State Isotopic Transient Kinetic Analysis experiments. Based on those experiments, a relation between C₅₊-selectivity and surface-coverages of CH _x -intermediates on cobalt was found.     

Direct-writing of PbS nanoparticles inside transparent porous silica monoliths using pulsed femtosecond laser irradiation

Pulsed femtosecond laser irradiation at low repetition rate, without any annealing, has been used to localize the growth of PbS nanoparticles, for the first time, inside a transparent porous silica matrix prepared by a sol-gel route. Before the irradiation, the porous silica host has been soaked within a solution containing PbS precursors. The effect of the incident laser power on the particle size was studied. X-ray diffraction was used to identify the PbS crystallites inside the irradiated areas and to estimate the average particle size. The localized laser irradiation led to PbS crystallite size ranging between 4 and 8 nm, depending on the incident femtosecond laser power. The optical properties of the obtained PbS-silica nanocomposites have been investigated using absorption and photoluminescence spectroscopies. Finally, the stability of PbS nanoparticles embedded inside the host matrices has been followed as a function of time, and it has been shown that this stability depends on the nanoparticle mean size.     

Bioactivity behaviour of biodegradable material comprising bioactive glass

Biocomposite of bioactive glass (BG) with chitosan polymer (CH) is prepared by freeze-drying technique. Obtained material is investigated by using several physico-chemical methods. The XRD and FTIR show the interface bonding interactions between glass and polymer. The specific surface and porosity of biocomposite were determined. In vitro assays were employed to evaluate the effect of chitosan addition on the glass by studying the chemical reactivity and bioactivity of the BG and BG/CH biocomposite after soaking in a simulated body fluid (SBF). The obtained results show the formation of a bioactive hydroxycarbonate apatite (HCA) layer and highlight the bioactivity and the kinetics of chemical reactivity of bioactive glass, particularly after association with chitosan. The BG/CH biocomposite has excellent ability to form an apatite layer. Inductively coupled plasma-optical emission spectrometry (ICP-OES) highlights the negative effect of chitosan on the silicon release toward the SBF of bioactive glass when in vitro assays.     

Processing of CaLa2S4 infrared transparent ceramics: A comparative study of HP and FAST/SPS techniques

The densification of CaLa₂S₄ (CLS) powders prepared by combustion method was investigated by the use of Field-Assisted Sintering Technique (FAST) and Hot Pressing (HP). CLS powders were sintered using FAST at 1000°C at different pressures and heating rates and sintered by HP under 120 MPa from 800°C to 1100°C for 6 hours with a heating rate of 10°C/min. Comparison of both techniques was further realized by use of the same conditions of pressure, dwell time, and heating rate. Complementary techniques (XRD, SEM-EDS, density measurements, FTIR spectroscopy) were employed to correlate the sintering processes/parameters to the microstructural/compositional developments and optical transmission of the ceramics. Both sintering techniques produce ceramics with submicrometer grain size and relative density of about 99%. Nevertheless, HP is more suitable to densify CLS ceramics without fragmentation and also reach higher transmission than FAST. Transmission of 40%–45% was measured out of a possible maximum of 69% based on the Fresnel losses in the 8-14 μm window when HP is applied at 1000°C for 6 hours under 120 MPa. In both techniques, ceramics undergo reduction issues that originate from graphitic sintering atmosphere.     

2-Methylthiazolidine and 4-ethylguaiacol,male sex pheromone components of the cockroachNauphoeta cinerea (dictyoptera,blaberidae): A reinvestigation

InNauphoeta cinerea, male calling behavior is associated with sex pheromone release by the sternal glands. The male pheromone that attracts females from a distance is a mixture of 2-methylthiazolidine and 4-ethylguaiacol. It is active at very low concentrations, 0.05 and 0.01 ng, respectively. Two other compounds, 3-hydroxy-2-butanone and 2-methyl-2thiazoline, act at close range, keeping the female in the vicinity of the male. The function of the volatile pheromone and those of previously described contact pheromones are discussed in regard to their possible involvement in the establishment of male dominant-subordinate relationships.     

Modélisation de l'efficacité de filtration d'un échangeur cyclone

This work is a modelling of the Aireco® filtration system. This heat exchanger, with particle catching capabilities, is made of a cyclonic body which contains refrigerated coils. The water vapour contained in the gas to be treated condensed on the coils surface. Our modelling considers two main capture surfaces: the entry zone in which particles are collected by inertial impaction and the cyclonic body in which particles diffused by centrifugal force is the main phenomena. We found that these considerations explain our experimental results with an accuracy more than 90%, when the Aireco® is on a normal point of working.     

Bases théoriques pour l’égalisation adaptative en mode autodidacte

Stability and convergence of adaptive algorithms are studied under a theoretical viewpoint, for the problem of discrete data transmission and their recovery by means of adaptive filtering (equalization). The relationships between adaptive equalization using a known training data sequence (training mode) and self-adaptive equalization using self-recovered data (self-learning mode) are pointed out. A comprehensive overview clarifies the satisfactory decaying behaviour of the transient error that is valid for both modes. Then stability of the self-learning mode is proved, under reasonable regularity conditions for the received signal at the channel output. Finally the self-learning equalizer, initiated with a short preamble in the training mode, is theoretically analyzed and its convergence towards optimality is proved, in agreement with practice.     

Conception assistée par ordinateur de circuits millimétriques incluant des discontinuités de type ligne à ailettes

Single and complex fin line discontinuities are precisely computed by means of the modal analysis combined with the spectral domain approach. Validity of the results is established by measurements of the scattering parameters of symmetrical configurations including these discontinuities in a «back to back» arrangement. Frequency dependent equivalent networks are derived and they can be used as data base in circuit simulation programs.     

Measuring error and sampling variation in stereology: comparison of the efficiency of various methods for planar image analysis

An evaluation is made of the relative efficiency (precision of the final estimate per unit time of measurement on a given set of sections) of different methods for planar analysis aimed at estimating aggregate, overall stereological parameters (such as V_v, S_v). The methods tested are point-counting with different densities of test points (4 ≤ P_T ≤ 900 per picture), semiautomatic computer image analysis with MOP and automatic image analysis with Quantimet, for obtaining V_v and S_v estimates. One biological sample as well as three synthetic model structures with known coefficients of variation between sections are used. The standard error of an estimate is mainly determined by the coefficient of variation between sampling units (= sections in the present paper) so that measuring each sample unit with a very high precision is not necessary. Automatic image analysis and point-counting with a 100-point grid were the most efficient methods for reducing the relative standard errors of the V_v and S_v estimates to equivalent levels in the synthetic models. Using a 64-point grid was as precise, and about 11 times faster than using a tracing device for obtaining the estimate of V_v in the biological sample.