Kinetic results and reaction pathways of intermolecular thiolato ligand migration between titanocene complexes and from Cp2TiX(SAr) (X=Cl, SAr) to PtCl(Me)(cod) (cod=η2,η2,-1,5-cyclooctadiene)

Article abstract of DOI:10.1246/bcsj.73.923

The mechanism of the thiolato ligand transfer from Cp₂Ti(X)(SAr) (X = Cl, SAr) to PtCl(Me)(cod) (cod = η², η²-1,5-cyclooctadiene) was established. The methyl ligand bonded to the Pt center acted as a spectator ligand throughout the reaction. Inertness of the methyl-Pt bond toward the reaction can be explained by a high degree of covalent character of the bond which inhibits ionic dissociation of the methyl ligand. Rapid and reversible disproportionation of Cp₂TiCl(SAr) type complexes to afford Cp₂Ti(SAr)₂ had an important role in the completion of the reaction. The resulting methyl(thiolato)platinum complexes with a labile cod ligand can be used as precursors of different organoplatinum complexes.