Diarylpalladium Complexes with a Cis Structure. Formation via Transmetalation of Arylboronic Acids with an Aryliodopalladium Complex and Intramolecular Coupling of the Aryl Ligands, Affording Unsymmetrical Biaryls

(2,4,6-Trifluorophenyl)- and (2,6-difluorophenyl)boronic acids react with PdI(C 6 H 4 O-4-Me)(tmen) (tmen = N,N,N ‘,N ‘ -tetramethylethylenediamine) in the presence of Ag 2 O to produce cis -diarylpalladium complexes with a tmen ligand via intermolecular transfer of the fluorophenyl group from B to Pd. The isolated complexes undergo coupling of the two aryl ligands upon heating the solution to 45−60 °C to afford unsymmetrical biaryls.