The chiral diphenylphosphinoxy P,N-ligands (+)-(2S,3R)-4-dimethylamino-3-methyl-1,2-diphenyl-2-diphenylphosphinoxybutan e (2) and (+)-(1S,2R)-2-dimethyl-amino-1-phenyl-1-diphenylphosphinoxy-propane (3) have been prepared starting from the corresponding aminoalcohols. The reactions of the already reported ligand 2-[1-phosphinoxy-1-(1S,2S,5R)-menthyl]pyridine (1) and of 2 and 3 with palladium(II) and platinum(II) substrates have been studied. The palladium complexes [Pd(1-3)Cl 2 ] have been used as catalytic precursors in the asymmetric Grignard cross-coupling reaction between 1-phenylethyl magnesium bromide and vinyl bromide. Some considerations on the low enantioselectivity found using the phosphinoxy P,N-ligands 1-3 are proposed. With the aim of verifying diastereoselectivity in the nucleophilic substitution reactions at palladium(II) and platinum(II) complexes containing the P,N-ligands 1-3, the reactions of the complexes 5, 6, 7 and 10 with the Grignard reagent PhMeCHMgBr, in the racemic form, have been unsuccessfully undertaken. The X-ray crystal structures of [Pt(3)(Ph 2 PO)Cl], 10, and of the oxide of 1 are also reported.