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Updated: Jul 11, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Insights into amine binding to biaryl phosphine palladium oxidative addition complexes and reductive elimination from
Timothy E Barder1, Stephen L Buchwald
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA. tbarder@mit.edu
Abstract:
We present results on the binding of a variety amines to monoligated oxidative addition complexes of the type L1Pd(Ar)Cl, where L is 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos, 1) or 2-dicyclohexylphosphino-2',4',6'-tri-ispropylbiphenyl (XPhos, 2). The binding of an amine to oxidative addition complexes composed of 1 and 2 is more complex than with smaller ligands as intermediate Pd(II) complexes with bulky biaryl phosphine ligands disfavor amine binding to favorable conformations of oxidative addition complexes. Additionally, thermodynamic and kinetic parameters for reductive elimination from complexes of the type L1Pd(amido)Ph (where amido = EtNH, Me2N, PhNH) are discussed. From this data, we suggest a possible mechanism for (biaryl phosphine) Pd-catalyzed amination reactions that is more intricate than previously thought.
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