title: Imidazol(in)ium hydrogen carbonates as a genuine source of N-heterocyclic carbenes (NHCs): applications to the facile preparation of NHC metal complexes and to NHC-organocatalyzed molecular and macromolecular syntheses.
abstract: Anion metathesis of imidazol(in)ium chlorides with KHCO(3) afforded an easy one step access to air stable imidazol(in)ium hydrogen carbonates, denoted as [NHC(H)][HCO(3)]. In solution, these compounds were found to be in equilibrium with their corresponding imidazol(in)ium carboxylates, referred to as N-heterocyclic carbene (NHC)-CO(2) adducts. The [NHC(H)][HCO(3)] salts were next shown to behave as masked NHCs, allowing for the NHC moiety to be readily transferred to both organic and organometallic substrates, without the need for dry and oxygen-free conditions. In addition, such [NHC(H)][HCO(3)] precursors were successfully investigated as precatalysts in two selected organocatalyzed reactions of molecular chemistry and polymer synthesis, namely, the benzoin condensation reaction and the ring-opening polymerization of d,l-lactide, respectively. The generation of NHCs from [NHC(H)][HCO(3)] precursors occurred via the formal loss of H(2)CO(3)via a concerted low energy pathway, as substantiated by Density Functional Theory (DFT) calculations.
authors.affiliation: Centre National de la Recherche Scientifique, Laboratoire de Chimie des Polymères Organiques, UMR 5629, 16 avenue Pey-Berland, F-33607 Pessac cedex, France.
authors.forename: Maréva
authors.initials: M
authors.lastname: Fèvre
authors.forename: Julien
authors.initials: J
authors.lastname: Pinaud
authors.forename: Alexandre
authors.initials: A
authors.lastname: Leteneur
authors.forename: Yves
authors.initials: Y
authors.lastname: Gnanou
authors.forename: Joan
authors.initials: J
authors.lastname: Vignolle
authors.forename: Daniel
authors.initials: D
authors.lastname: Taton
authors.forename: Karinne
authors.initials: K
authors.lastname: Miqueu
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Sotiropoulos