Complexation of the chiral P,N-bidentate ferrocene- and cymantrene-based iminoarylphosphites with [Rh(CO)(2)O-12, [Rh(COD)(THF)(2)]BF4, [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)(eta(2)-PN)Cl], [Rh(COD)(eta(2)-PN)]BF4, [M(allyl)(eta(2)-PN)]BF4 (M = Pd, Pt) and cis-[M(eta(2)-PN)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. (c) 2006 Elsevier B.V. All rights reserved.