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Anna M. Maj Albert Demonceau Alfred F. Noels 《Journal of organometallic chemistry》2007,692(14):3048-3056
A range of new imidazolium and imidazolinium chlorides bearing biphenyl units on their nitrogen atoms was synthesized. They differed by the electron-withdrawing or -donating nature and the steric bulk of the substituents on their aromatic rings. These various N-heterocyclic carbene (NHC) precursors were combined with the [RuCl2(p-cymene)]2 dimer and potassium tert-butoxide to generate the corresponding ruthenium-arene complexes [RuCl2(p-cymene)(NHC)] in situ. The catalytic activity of these species was investigated in the photoinduced ring-opening metathesis polymerization (ROMP) of cyclooctene. The results obtained confirmed the necessity of blocking the ortho-positions of the phenyl rings in the vicinity of the metal center in order to attain high catalytic efficiencies. They also showed that changing the steric and electronic properties of the substituents on the remote phenyl rings of the biphenyl units had no significant influence on the outcome of the polymerization. 相似文献
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Tutusaus O Viñas C Núñez R Teixidor F Demonceau A Delfosse S Noels AF Mata I Molins E 《Journal of the American Chemical Society》2003,125(39):11830-11831
exo-Cluster dicarbollides substitution has allowed tuning of the E degrees (Ru(II)/Ru(III)) potential to obtain the best-performing Kharasch catalyst. We postulate that this is possible through the to-and-fro electron movement between the boron cluster and the sulfonium moieties. 相似文献
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Simal F Delfosse S Demonceau A Noels AF Denk K Kohl FJ Weskamp T Herrmann WA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(13):3047-3052
Air-stable and readily available ruthenium benzylidene complexes of the general type [RuCl2(=CHPh)(L)(L')] (L, L' = PCy3 and/or N-heterocyclic carbene) constitute a new class of catalyst precursors for atom-transfer radical polymerization (ATRP) of methyl methacrylate and styrene, and provide an unprecedented example for the involvement of ruthenium alkylidenes in radical reactions. They promote the polymerization of various monomers with good to excellent yields, and in a controlled way with methyl methacrylate and styrene. Variations of their basic structural motif provide insights into the essential parameters responsible for catalytic activity. The ligands L (PCy3 and/or N-heterocyclic carbene) turned out to play a particularly important role in determining the rate of the polymerizations. A similarly pronounced influence is exerted by the substituents on the N-heterocyclic carbene. Our results indicate that the catalysts decompose quickly under ATRP conditions, and polymerizations are mediated by both [RuCl2(=CHPh)(L)(L')] complexes and ruthenium species bereft of the benzylidene moiety, through a pathway in which both tricyclohexylphosphane and/or N-heterocyclic carbene ligands remain bound to the metal center. Polymerization of n-butyl acrylate and vinyl acetate is not controlled and most probably takes place through a redox-initiated free-radical process. 相似文献
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Franois Simal Albert Demonceau Alfred F. Noels 《Angewandte Chemie (International ed. in English)》1999,38(4):538-540
A new set of ruthenium complexes such as 1 and 2 (the Grubbs ruthenium–carbene complex) has been shown to mediate the controlled atom‐transfer radical polymerization (ATRP) of vinyl monomers with exceptional efficiency. Furthermore, there is a striking parallelism between the catalytic activity of these compounds in olefin metathesis and in ATRP. 相似文献
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This paper presents an incremental-secant mean-field homogenization (MFH) procedure for composites made of elasto-plastic constituents exhibiting damage. During the damaging process of one phase, the proposed method can account for the resulting unloading of the other phase, ensuring an accurate prediction of the scheme. When strain softening of materials is involved, classical finite element formulations lose solution uniqueness and face the strain localization problem. To avoid this issue the model is formulated in a so-called implicit gradient-enhanced approach, with a view toward macro-scale simulations. The method is then used to predict the behavior of composites whose matrix phases exhibit strain softening, and is shown to be accurate compared to unit cell simulations and experimental results. Then the convergence of the method upon strain softening, with respect to the mesh size, is demonstrated on a notched composite ply. Finally, applications consisting in a stacking plate, successively without and with a hole, are given as illustrations of the possibility of the method to be used in a multiscale framework. 相似文献
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[RuCl2(p-cymene)] complexes containing triarylphosphine ligands with various substituents at the para position were used to catalyse the atom transfer radical addition of carbon tetrachloride to various olefins, and their catalytic activities were nicely correlated with their electrochemical parameters. 相似文献
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L. Beaufort F. Benvenuti A.F. Noels 《Journal of molecular catalysis. A, Chemical》2006,260(1-2):210-214
The synthesis of a new series of 2,6-bis(imino)pyrazinyl ligands, [ArNCPyzCNAr] where the aryl groups Ar = naphtyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, and their iron(II) complexes is described starting from monoacetylpyrazine. 相似文献