Two dianionic amine bis(thiolato) ligands are introduced and their reactions with titanium tetra(iso-propoxide) studied; ligand N2H2S2H2 (1) having NH donor groups leads exclusively to dinuclear [{Ti(N2H2S2)(OiPr)}2] (2) along with an oxidation product of the ligand (3) whereas ligand N2Me2S2H2 (4) having an additional N-substituent leads exclusively to a mononuclear [Ti(N2Me2S2)(OiPr)2)] (5) type complex.