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