Azavinylidenephosphoranes: A Class of Cyclic Push–Pull Carbenes

Florie Lavigne, Aimée El Kazzi, Yannick Escudié, Eddy Maerten, Tsuyoshi Kato, Nathalie Saffon-Merceron, Vicenç Branchadell, Fernando P. Cossío, Antoine Baceiredo

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7 Citations (Scopus)


© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The synthesis of a novel family of cyclic push–pull carbenes, namely, azavinylidene phosphoranes, is described. The methodology is based on a formal [3+2] cycloaddition between terminal alkynes and phosphine–imines followed by an oxidation/deprotonation step. Carbenes 6, obtained by simple deprotonation, exhibit typical transient carbene reactivity like the intramolecular CH insertion reaction and a pronounced ambiphilic character exemplified by [2+1] cycloaddition with electron-poor methyl acrylate. Owing to the cyclic structure, carbenes 6 also exhibit an excellent coordination ability toward transition metals. RhIcomplex 10 was obtained in excellent yield and was fully characterized by multinuclear NMR spectroscopy and X-ray crystallography. The corresponding RhI–carbonyl complex was also prepared; this indicates that carbenes 6 belong to the strongest σ-donating ligands to date. DFT calculations confirmed the high σ-donation ability of 6 and their classification as push–pull carbenes with a relatively small singlet–triplet energy gap of 23.2–24.3 kcal mol−1.
Original languageEnglish
Pages (from-to)12528-12536
JournalChemistry - A European Journal
Issue number39
Publication statusPublished - 1 Jan 2014


  • carbene ligands
  • carbenes
  • density functional calculations
  • synthetic methods
  • ylides


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