Complexation of the chiral P, N-bidentate ferrocene- and cymantrene-based iminoarylphosphites with [Rh(CO) 2Cl] 2, [Rh(COD)(THF) 2]BF 4, [Pd(allyl)Cl] 2, [Pt(allyl)Cl] 4, [Pd(COD)Cl 2] and [Pt(COD)Cl 2] was found to give chelate complexes [Rh(CO)(η 2-P,N)Cl], [Rh(COD)(η 2-P,N)]BF 4, [M(allyl)(η 2-P,N)]BF 4 (M = Pd, Pt) and cis-[M(η 2-P,N)Cl 2] (M = Pd, Pt), correspondingly. With the new P, N-ligands, up to 97% ee was achieved in the asymmetric Pd-catalysed alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. In the enantioselective amination of 1,3-diphenyl-2-propenyl acetate with sodium diformylamide, up to 96% enantioselectivity was achieved.