Synthesis, electrochemical properties and reactivity of [Fe(η5-C5H4PPh2)2]Pt(benzenethiolate)2 complexes: X-ray crystal structure of [Fe(η5-C5H4PPh2)2]Pt(SC6HF4)2

Three heteroleptic Pt(II) complexes with 1,1′-bis(diphenylphosphino)ferrocene (dppf) and benzene-monothiolate (BzT) ligands such as benzenethiolate (BT), 2,3,5,6-tetrafluorobenzenethiolate (TFBT) and 3,5-dimethylbenzenethiolate (DMBT), (dppf)Pt(BzT)2, were synthesized from (dppf)PtCl2 and the corresponding benzene-monothiols. X-ray structural analysis of (dppf)Pt(TFBT)2 showed that the two TFBT ligands are parallel and in an anti-conformation with respect to a slightly distorted P2PtS2 plane. The redox properties of the three Pt(II) complexes are correlated with the electron-donating capability of the monothiolate ligands. The more-electronegative TFBT ligand induces a short Pt–P bond distance (2.273(2) Å), a large Pt–P coupling constant (JPt–P = 3171 Hz) and a high oxidation potential (image). A charge-transfer complex of (dppf)Pt(DMBT)2 was prepared by the reaction with F4TCNQ and characterized.