Coinage metal-NHC complexes : Synthesis, functionalization and applications in aqueous or protic media
Mardi 21 novembre 2017 11:00
- Duree : 1 heure
Lieu : Salle d’accueil du CEA-Grenoble
Orateur : Frederico CISNETTI (Organometallics group, Institut de Chimie de Clermont-Ferrand)
The functionalization of metal N-heterocyclic carbene (NHC) complexes is a research topic actively explored by numerous groups worldwide, due to the ubiquity of this ligand class in catalysis, and more recently in biomedical applications (1). In this presentation, some results pertaining to the catalytic applications of functionalized coinage-metal-NHC complexes deriving from azide-tagged NHC precursors will be discussed. A connected topic, metalation reactions for copper(I)- and silver(I)- NHC complexes in aqueous ammonia will also be presented (2).and some biological results will be discussed (3).
The development of simple and modular syntheses to introduce an azide moiety on NHC precursors either in close proximity of a (pre)carbenic center or in a distant site will be described. These compounds allowed the preparation of pre- and post-functionalized metal complexes. For the latter, a so- called “autoclick’ process was possible in which copper-NHC complexes were able to catalyze their own functionalization without any external catalyst, albeit in an intermolecular manner (4).
Prefunctionalized copper- and gold- NHC complexes with ligands modified to ensure a high solubility in water will be presented. Their applications as catalysts in mild aqueous conditions for azide-alkyne cycloaddition (5) and alkyne hydration (6), respectively, will be detailed. Finally, while attempting to prepare NHC-N3 chelates from N-(2-azidophenyl) azolium salts, an unexpected NHC-nitrene cyclisation occurs when these derivatives are subjected to conditions in which copper(I)-NHC complexes are formed. This reaction was optimized to provide an efficient access to fused nitrogen heterocycles (7).
(1) O. Kuhl, Functionalized N-heterocyclic carbene complexes, 2010, Wiley (Chichester)
(2) C. Gibard et al., Organometallics, 2013, 32, 4279. C. Gibard et al., J. Organomet. Chem., 2017, 840, 2932.
(3) T. Bernardi et al., ChemMedChem., 2014, 1140
(4) H. Ibrahim et al., Dalton Trans., 2014, 43, 6981
(5) Gaulier et al., Chem. Commun., 2012, 48, 4005.
(6) H. Ibrahim et al., Adv. Synth. Catal., 2015, 357, 3893.
(7) K. Fauché et al., Chem. Commun., 2017, 53, 2402
Contact : odile.rossignol@cea.fr
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