The compounds of general formula [ML2](ClO4)2 [M = Cu(II), Ni(II), Co(II)]; L = diethyl 3-pyridylmethyl[N-(butyl)amino]phosphonate (3-pmape) or diethyl 4-pyridylmethyl[N-(butyl)amino]phosphonate (4-pmape) were prepared. The new complexes were identified and characterized by elemental analysis, infrared, electronic spectral studies and magnetic measurements. The complexes are sixcoordinate. Metal ions are octahedrally surrounded by two pyridine and two amine nitrogens, and two oxygens of the phosphoryl groups. The results of the magnetic studies suggest polymeric chain structure of the above complexes and indicate weak antiferromagnetic interaction between the magnetic centers. The magnetic behavior of Co(II) complexes is characteristic for cobalt(II) system with an important orbital contribution via spin-orbit coupling.