Synthesis and crystal structure of a diplatinum cyclopentadienyldiphenylphosphine sulphide bridged complex

The mixed early–late TiPt2 compound [(η5-C5H4SiMe3)Ti(μ3-1η5-C5H4P(S)Ph2-2,3κS)(μ-SPh)2{Pt(C6F5)2}2] (3) containing a functionalised thiophosphorylcyclopentadienyl SPPh2C5H4 bridging ligand has been obtained by reaction of [(η5-C5H4SiMe3)(η5-C5H4P(S)Ph2)Ti(SPh)2] (1) with 2 equivalents of cis-[Pt(C6F5)2(thf)2]. The crystallisation of 3 in CH2Cl2/MeOH at −20°C gave the unexpected diplatinum complex [Pt(C6F5)2(μ-SPPh2C5H5)]2 (4) with an unusual double bis-cyclopentadienyldiphosphine sulphide bridging system (μ-κS), which has been characterised by X-ray diffraction. As an alternative route to the synthesis of 4 the reaction of cis-[Pt(C6F5)2(thf)2] with SPPh2C5H5 has been studied. Independently of the stoichiometry employed, this reaction gives mixtures of 4 and the novel mononuclear complex cis-[Pt(C6F5)2(SPPh2C5H5)2] (6). Low temperature control of this reaction indicates that both complexes (4 and 6) are formed through a common intermediate identified as cis-[Pt(C6F5)2(SPPh2C5H5)(thf)] (5) on the basis of spectroscopic techniques.