Synthesis, electrochemical properties and reactivity of [Fe( η 5-C 5H 4PPh 2) 2]Pt(benzenethiolate) 2 complexes: X-ray crystal structure of [Fe( η 5-C 5H 4PPh 2) 2]Pt(SC 6HF 4) 2

• Published in: Inorganic chemistry communications 2010, Vol.13 (1), p.183-186
• Main Authors: Lee, Su-Kyung, Noh, Dong-Youn
• Format: Article
• Language: English
• Subjects: Benzenethiolate; Electrochemistry; Pt(II) complex; X-ray crystal structures
• ISSN: 1387-7003; 1879-0259
• DOI: 10.1016/j.inoche.2009.11.010

The redox properties of three heteroleptic Pt(II) complexes were investigated: [Fe(C 5H 4PPh 2) 2]Pt(BzT) 2 where BzT = benzenethiolate (BT), 2,3,5,6-tetrafluorobenzenethiolate (TFBT) and 3,5-dimethylbenzenethiolate (DMBT), correlating with the electron-withdrawing capability of the monothiolate ligands. 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)PtCl 2 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 P 2PtS 2 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 ( 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.