Novel heterobimetallic titanium-platinum complexes. Crystal structure of [(eta(5)-C5H4SiMe3)(SPh)Ti(mu,eta(5)-kappa S-C5H4P(S)Ph-2)(mu-SPh)Pt(C6F5)(2)]

The thiophosphorylcyclopentadienyl-thiolate complexes [(eta(5)-C5H4R)(eta(5 )-C5H4P(S)Ph-2)Ti(SPh)(2)] react with cis-[Pt(C6F5)(2)(THF)(2)] initially g ive the adducts [(eta(5)-C5H4R)(SPh)Ti(mu,eta(5)-kappa S-C5H4P(S)Ph-2)(mu-S Ph)Pt(C6F5)(2)] [R = P(S)Ph-2 (1); SiMe3 (4)], which finally rearrange in s olution to form the double thiolate-bridged derivatives [(eta(5)-C5H4R)(eta (5)-C5H4P(S)Ph-2)Ti(mu-SPh)(2)Pt(C6F5)(2)] [R = P(S)Ph-2 (2) (syn); SiMe3 ( 5) (syn/anti)]. This paper presents the crystal structure of 4, a complex d isplaying an unusual mixed thiolate-thiophosphorylcyclopentadienyl bridging system. In contrast, similar reactions of cis-[Pt(C6F5)(2)(THF)(2)] with [ (eta(5)-C5H4R)(eta(5)-C5H4P(O)Ph-2)Ti(SPh)(2)] (R = P(O)Ph-2; SiMe3) only g ives [(eta(5)-C5H4R)(eta(5)-C5H4P(O)Ph-2)Ti(mu-SPh)(2)Pt(C6F5)(2)] [R = P(O )Ph-2 (3) (syn); SiMe3 (6) (syn/anti mixtures)] as expected due to the soft acid nature of the platinum centre. (C) 1999 Elsevier Science S.A. All rig hts reserved.