Structural and electronic features of the novel title sulfur-oxygen donor ligand Me2pipto (1), are discussed in comparison with those of the corresponding dithione ligand Me2pipdt. A tuning of the electronic and coordination properties of the ligand, relatable to the soft/hard power of the donor atoms, is achieved. Coordination properties have been checked towards Ni (II) and Fe (III) cations obtaining [Ni (Me2pipto) 3](BF4) 2 (2) and [Fe (Me2pipto) 3](BF4) ...