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Updated: Jun 14, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Gas-phase energetics of reductive elimination from a palladium(II) N-heterocyclic carbene complex
Erik P A Couzijn1, Eva Zocher, Andreas Bach
1Laboratorium für Organische Chemie, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland.
Abstract:
Energy-resolved collision-induced dissociation experiments using tandem mass spectrometry are reported for an phenylpalladium N-heterocyclic carbene (NHC) complex. Reductive elimination of an NHC ligand as a phenylimidazolium ion involves a barrier of 30.9(14) kcal mol(-1), whereas competitive ligand dissociation requires 47.1(17) kcal mol(-1). The resulting three-coordinate palladium complex readily undergoes reductive C-C coupling to give the phenylimidazolium pi complex, for which the binding energy was determined to be 38.9(10) kcal mol(-1). Density functional calculations at the M06-L//BP86/TZP level of theory are in very good agreement with experiment. In combination with RRKM modeling, these results suggest that the rate-determining step for the direct reductive elimination process switches from the C-C coupling step to the fragmentation of the resulting sigma complex at low activation energy.
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