Ferrocene-based chiral dinuclear thiolato-bridged complexes of Pd(II) and Pt(II)

A series of ferrocene-based chiral dinuclear complexes of Pd(II) and Pt(II), containing the deprotonated form of the ligand (R)-1-[(S)-diphenylphosphino) ferrocenyl] ethyl mercaptan (1-H), have been prepared. These complexes, [PdX(1-H)](2) (X = Cl, Br, I, CNBut (CF3SO3 salt), CNCH2CO2CH3 (CF3SO3 and PF6 salts), SnCl3) and [PtX(1-H)](2) (X=Cl, Br, I, SnCl3 are bridged by the two sulfur atoms. The structures of two palladium derivatives, 2a, X = Cl and 4a, X = CNBut have been determined by X-ray diffraction methods. Both complexes reveal strongly hinged Pd2S2 rings, i.e, they show 39 and 50 degrees angles between the two coordination planes within the complexes, in contrast to expectations based on calculations. The molecules have the symmetrical-trans structure and syn sulfur substituents. (C) 1997 Elsevier Science S.A.