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

Maréva Fèvre, Julien Pinaud, Alexandre Leteneur, Yves Gnanou, Joan Vignolle*, Daniel Taton, Karinne Miqueu, Jean Marc Sotiropoulos

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

124 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)6776-6784
Number of pages9
JournalJournal of the American Chemical Society
Volume134
Issue number15
DOIs
StatePublished - Apr 18 2012

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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