The complex formation of Cd(II) with N-donor ligands in dimethylsulfoxide (DMSO) is investigated by means of potentiometry and titration calorimetry. The ligands considered in this work are tripodal polyamines and polypyridines: 2,2',2 ''-triaminotriethylamine (TREN), tris (2-( methylamino) ethyl) amine (Me(3)TREN), tris(2-(dimethylamino) ethyl) amine (Me(6)TREN), tris[(2-pyridyl) methyl] amine (TPA) and 6,6'-bis-[bis-(2-pyridylmethyl)aminomethyl]-2,2'-bipyridine (BTPA). These ligands are characterized by a systematic modification of the donor groups to relate their structure to the thermodynamics of the complexes formed. The TREN and Me(3)TREN ligands form highly stable species. The stability of the complex formed with the fully methylated Me(6)TREN is much lower than with other polyamines and the enthalpic and entropic terms suggest an incomplete coordination to the metal ion. In general, the TPA ligand forms complexes less stable than TREN and Me(3)TREN as a result of the combination of higher structural rigidity of TPA and lower basicity of pyridine moiety with respect to primary and secondary amines. Pyridine-containing ligands display, in general, a less unfavorable formation entropy than tripodal polyamines here considered. In particular, TPA forms a more stable 1: 1 species with respect to Me(6)TREN due to the entropic term, being the enthalpy less negative. The ligand BTPA is able to form only a monometallic complex, where the metal ion is likely to be encapsulated as indicated by the obtained thermodynamic parameters.
