The complexes formed by combining Pd(OAc)(2) and iminophosphine ligands (P (N) over cap) are active catalysts in Suzuki-Miyaura cross-coupling reactions under mild conditions. Aryl bromides and iodides, as well as benzyl chlorides give the corresponding coupled products in high yields at low temperatures (25-50 degrees C) using these catalysts. Iminophosphines containing the most sterically demanding groups attached to the N-imino moiety were the most effective ligands. New divalent Pd complexes of known iminophosphines were synthesised and their activity was compared with the in situ generated catalyst system. The complex resulting from the oxidative addition of 4-bromo anisole [Pd(4-CH3OC6H4)Br(P (N) over cap)] was more active than the in situ generated system. However, palladacycles containing the iminophosphine ligand (e.g., {[C6H4CH(Me)(2)St-Bu]Pd(PN)}+PF6-) were less active than the in situ generated catalyst due to the greater stability of the complexes that involve two bidentate ligands. Poisoning tests demonstrated that homogeneous mononuclear palladium species containing the iminophsophine ligand were responsible for the catalytic activity. (C) 2009 Elsevier B.V. All rights reserved.