Catalyse par des complexs σ-aryl-nickel de l'electroreduction en biaryles des halogenures aromatiques

In mixed THF/HPMA, electrochemical reduction of NiX₂L₂ (L = PPh₃, X = Cl or Br) yields a zerovalent nickel complex which reacts very rapidly with ArX (X = I, Br, Cl) by oxidative addition to give ArNiXL₂, which also is electroreducible. Thus it is possible to obtain a catalytic electroreduction of ArX which affords mainly biaryls when X = Cl. A mechanism is suggested according the various results especially with a view to explain the loss of catalytic activity. A clear indication of increasing activity is given when aliphatic bromides are added to the solutions.     

Chemical analysis of polymers using transmission electron microscopy/electron energy-loss spectroscopy: The example of poly(ethylene terephthalate)

We have performed EELS analysis of poly (ethylene terephthalate) (PET) in the analytical TEM in order to evaluate the possibility to obtain chemical analysis of the polymer at sub-micrometer scale. Due to irradiation damage, it revealed necessary to work at the lowest possible electron dose, typically below 10³ C.m⁻², and with the specimen cooled to liquid nitrogen temperature. In the acquired spectra, we propose an identification of the different chemical bondings in agreement with XANES experiments.