Aminophosphine ligands: synthesis, coordination chemistry, and activity of their palladium(II) complexes in Heck and Suzuki cross-coupling reactions

Abstract

The reaction of 4-aminodiphenylamine or 2-aminofluorene with two equivalents of PPh2Cl in the presence of Et3N gives new bis(diphenylphosphino)amines N,N-bis(diphenylphosphino)-4-aminodiphenylamine 1 and N,N-bis(diphenylphosphino)-2-aminofluorene 2 in good yields. Oxidation of 1 or 2 with hydrogen peroxide, elemental sulfur or gray selenium affords the corresponding chalcogen derivatives. The palladium and platinum complexes of these P–N–P donor ligands were prepared by the reaction of the bis(phosphino)amines with MCl2(cod) (M = Pd or Pt, cod = cycloocta-1,5-diene). All the new compounds have been characterized by analytical and spectroscopic methods, including 1H-31P NMR, 1H-13C HETCOR, or 1H-1H COSY correlation experiments. The Pd(II) complexes were investigated as catalysts in the Suzuki and Heck reactions; both showed good catalytic activity affording high yields of the desired products.