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Piedra-Arroni E.,CNRS Laboratory for Basic and Applied Heterochemistry | Ladaviere C.,University Claude Bernard Lyon 1 | Amgoune A.,CNRS Laboratory for Basic and Applied Heterochemistry | Bourissou D.,CNRS Laboratory for Basic and Applied Heterochemistry
Journal of the American Chemical Society | Year: 2013

Dual systems combining Zn(C6F5)2 with an organic base (an amine or a phosphine) promote the controlled ring-opening polymerization of lactide and ε-caprolactone. The Lewis pairs cooperate to activate the monomers, affording well-defined high molecular weight cyclic polyesters. Efficient chain-extension gives access to cyclic block copolymers. © 2013 American Chemical Society.


Chahdoura F.,CNRS Laboratory for Basic and Applied Heterochemistry | Favier I.,CNRS Laboratory for Basic and Applied Heterochemistry | Gomez M.,CNRS Laboratory for Basic and Applied Heterochemistry
Chemistry - A European Journal | Year: 2014

This Minireview considers the foremost reported works involving glycerol as a solvent in the synthesis of organometallic complexes and metallic nanoparticles. This analysis highlights their catalytic applications. A special emphasis is devoted to the ability of glycerol to immobilize nanometric species, which, in turn, enables an efficient recycling of the catalytic phase to give metal-free organic products. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


Destarac M.,Toulouse 1 University Capitole | Destarac M.,CNRS Laboratory for Basic and Applied Heterochemistry
Macromolecular Reaction Engineering | Year: 2010

The extraordinary scientific development of controlled radical polymerization (CRP) contrasts with the very limited number of commercially available products derived from these technologies. The present comprehensive survey takes up existing public knowledge on industrial features of CRP and gives a critical point of view on its global status, and on each CRP technique in particular. The main techniques, namely RAFT/MADIX, NMP, ATRP, OCRP, OHRP and (R)ITP, are introduced. The focus is put on their current status in industry, based on selected patent literature, conference proceedings, professional press releases and technical data sheets of commercial products. This includes the industrial availability of CRP agents, the types of polymers that have been already commercialized or that are at an advanced stage of development, and the related applications and markets. The strengths and weaknesses are given for the different CRP techniques, and ways of improvements are suggested. As is often the case for strong technological breakthroughs, the CRP processes face a multitude of hurdles (at different degrees depending on the type of CRP), that must be overcome and which greatly increase the time-tomarket for polymer products compared to mature technologies. In spite of its slow development, CRP is seen as a revolutionary method to produce precisely controlled, next generation specialty polymer additives and materials. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


Liao Q.,CNRS Laboratory for Basic and Applied Heterochemistry | Saffon-Merceron N.,University Paul Sabatier | Mezailles N.,CNRS Laboratory for Basic and Applied Heterochemistry
Angewandte Chemie - International Edition | Year: 2014

Stoichiometric reduction of N2 at a Mo center stabilized by a bulky tetradentate phosphine ligand (PP3 Cy) allowed isolation of Mo-imidoamine and Mo-imido complexes. Both complexes as well as the MoII precursor are equally suitable catalysts for the synthesis of NTMS3 (TMS= trimethylsilyl) from N2, TMSCl, and electron sources. Mechanistic studies prove the involvement of a TMS radical at least in one of the catalytic steps. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.


Destarac M.,CNRS Laboratory for Basic and Applied Heterochemistry
Polymer Reviews | Year: 2011

There are a certain number of precautions a polymer chemist should take before undertaking a reversible addition-fragmentation chain transfer (RAFT) polymerization with a view of obtaining a polymer with controlled macromolecular characteristics (M̄n, PDI) and little or no change of rate of polymerization in comparison with conventional radical polymerization. Among them, a proper selection of the so-called R and Z groups borne by the thiocarbonyl thio skeleton of the RAFT agent is essential and is strongly dependent on the considered monomer. In this review, we introduce the basic concepts associated with the RAFT process like its mechanism and kinetics, and how the RAFT agent structure can strongly influence its reactivity and sometimes lead to undesired kinetic behaviors. © Taylor & Francis Group, LLC.


Bratko I.,CNRS Laboratory for Basic and Applied Heterochemistry | Gomez M.,CNRS Laboratory for Basic and Applied Heterochemistry
Dalton Transactions | Year: 2013

In an eco-friendly development, catalysis represents the key approach for converting raw materials into valuable products, particularly convenient for multi-step transformations. Mimicking Nature seems the smartest way to design poly-functional assemblies leading to the design of "synergic" catalysts. This perspective focuses on the advances in the conception of polymetallic catalysts bonded to a single ligand frame. This journal is © The Royal Society of Chemistry 2013.


Beija M.,CNRS Laboratory for Molecular and Photochemical Reactions | Marty J.-D.,CNRS Laboratory for Molecular and Photochemical Reactions | Destarac M.,CNRS Laboratory for Basic and Applied Heterochemistry
Chemical Communications | Year: 2011

Narrowly distributed poly(N-vinyl caprolactam) obtained by the MADIX/RAFT process was used for the preparation of novel thermoresponsive gold nanoparticles presenting a sharp reversible response to temperature, which can be easily modulated near the physiological temperature by simply changing the polymer molecular weight or concentration. © The Royal Society of Chemistry.


Amgoune A.,Toulouse 1 University Capitole | Amgoune A.,CNRS Laboratory for Basic and Applied Heterochemistry | Bourissou D.,Toulouse 1 University Capitole | Bourissou D.,CNRS Laboratory for Basic and Applied Heterochemistry
Chemical Communications | Year: 2011

The ability of Lewis acids to coordinate to transition metals as σ-acceptor ligands was recognized as early as in the 1970's, but so-called Z-type ligands remained curiosities until the early 2000's. Over the last decade, significant progress has been made in this area, especially via the incorporation of Lewis acid moieties into multidentate, ambiphilic ligands. Our understanding of the nature and influence of TM → Z interactions has considerably improved and the scope of Lewis acids susceptible to behave as σ-acceptor ligands has been significantly extended. This feature article summarizes these recent achievements.


Joost M.,CNRS Laboratory for Basic and Applied Heterochemistry | Joost M.,VU University Amsterdam | Amgoune A.,CNRS Laboratory for Basic and Applied Heterochemistry | Bourissou D.,CNRS Laboratory for Basic and Applied Heterochemistry
Angewandte Chemie - International Edition | Year: 2015

For a while, the reactivity of gold complexes was largely dominated by their Lewis acid behavior. In contrast to the other transition metals, the elementary steps of organometallic chemistry - oxidative addition, reductive elimination, transmetallation, migratory insertion - have scarcely been studied in the case of gold or even remained unprecedented until recently. However, within the last few years, the ability of gold complexes to undergo these fundamental reactions has been unambiguously demonstrated, and the reactivity of gold complexes was shown to extend well beyond π-activation. In this Review, the main achievements described in this area are presented in a historical context. Particular emphasis is set on mechanistic studies and structure determination of key intermediates. The electronic and structural parameters delineating the reactivity of gold complexes are discussed, as well as the remaining challenges. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


Bouhadir G.,CNRS Laboratory for Basic and Applied Heterochemistry | Bourissou D.,CNRS Laboratory for Basic and Applied Heterochemistry
Chemical Society Reviews | Year: 2016

Since the mid 2000's, the incorporation of Lewis acid moieties in ligands for transition metals has been studied extensively. So-called ambiphilic ligands were shown to possess rich and unusual coordination properties and special focus was given to the coordination of Lewis acids as σ-acceptor ligands (concept of Z-type ligands). Recent studies have demonstrated that the presence of Lewis acids at or nearby transition metals can also strongly impact their reactivity. These results are surveyed in this review. The stoichiometric transformations and catalytic applications of complexes deriving from ambiphilic ligands are presented. The different roles the Lewis acid can play are discussed. © 2016 The Royal Society of Chemistry.

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