The preparation of a series of Pd(II) and Pt(II) derivatives with three N,O hybrid ligands 1-(2-pyridyl)ethyldiphenylphosphine oxide, L1; (2-pyridyl)methyldiphenylphosphine oxide, L2 and 2-pyridyldiphenylphosphine oxide, L3 is described. Depending on the ligand to metal molar ratio, either 1∶1 [LMCl2] {[L1PdCl2] 1, [L2PdCl2] 2, [L3PdCl2] 3, [L1PtCl2] 4} or 2∶1 [L2MCl2] {[L12PdCl2] 5, [L22PdCl2] 6, [L12PtCl2] 7} adducts are obtained. In addition, an ionic species [L12Pd][PF6]2 8, has been isolated by treatment of complex 5 with AgPF6. The structures in the solid state of compounds 5b·MeOH·H2O, 6·MeOH and 4·CH2Cl2 have been solved by X-ray diffraction. The structures of trans-[L12PdCl2] 5b (one of the diastereomers of 5) and trans-[L22PdCl2] 6 are rather different, the former being a chiral molecule (R,R enantiomer) with a C2 axis perpendicular to the plane of the metal, the latter, 6, being a centrosymmetric molecule. In both the species the ligand is bonded through the nitrogen atom. In complex [L1PtCl2] 4, the ligand is coordinated through the N and O atoms to form a six-membered ring which adopts a boat-like conformation. The structure reveals a fairly short interaction between one hydrogen atom of the Me group in an axial position and the platinum atom, Pt · · · H 2.69 Å. Short contacts Pd · · · H are also observed in the structures of compounds 5b and 6. Some aspects of the reactivity of the new species are discussed.