Novel heterobimetallic titanium–platinum complexes. Crystal structure of [(η5-C5H4SiMe3)(SPh)Ti(μ,η5-κS-C5H4P(S)Ph2)(μ-SPh)Pt(C6F5)2]

The thiophosphorylcyclopentadienyl-thiolate complexes [(η5-C5H4R)(η5-C5H4P(S)Ph2)Ti(SPh)2] react with cis-[Pt(C6F5)2(THF)2] initially give the adducts [(η5-C5H4R)(SPh)Ti(μ,η5-κS-C5H4P(S)Ph2)(μ-SPh)Pt(C6F5)2] [R=P(S)Ph2 (1); SiMe3 (4)], which finally rearrange in solution to form the double thiolate-bridged derivatives [(η5-C5H4R)(η5-C5H4P(S)Ph2)Ti(μ-SPh)2Pt(C6F5)2] [R=P(S)Ph2 (2) (syn); SiMe3 (5) (syn/anti)]. This paper presents the crystal structure of 4, a complex displaying an unusual mixed thiolate-thiophosphorylcyclopentadienyl bridging system. In contrast, similar reactions of cis-[Pt(C6F5)2(THF)2] with [(η5-C5H4R)(η5-C5H4P(O)Ph2)Ti(SPh)2] (R=P(O)Ph2; SiMe3) only gives [(η5-C5H4R)(η5-C5H4P(O)Ph2)Ti(μ-SPh)2Pt(C6F5)2] [R=P(O)Ph2 (3) (syn); SiMe3 (6) (syn/anti mixtures)] as expected due to the soft acid nature of the platinum centre.