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 benzenemonothiolate (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-con formation 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) angstrom), a large Pt-P coupling constant (J(Pt-P) = 3171 Hz) and a high oxidation potential (E-pa(3) = 1.355 V). A charge-transfer complex of (dppf)Pt(DMBT)(2) was prepared by the reaction with F4TCNQ and characterized. (C) 2009 Elsevier B.V. All rights reserved.