Novel heterobimetallic titanium-platinum complexes. Crystal structure of [(#eta#~5-C_5H_4SiMe_3)(SPh)Ti(#mu#,#eta#~5-kS-C_5H_4P(S)Ph_2)(#mu#-SPh)Pt(C_6F_5)_2]

摘要

The thiophosphorylcyclopentadienyl-thiolate complexes [(#eta#~5-C_5H_4R)(#eta#~5-C_5H_4P(S)Ph_2)Ti(SPh)_2] react with cis-[Pt(C_6F_5)_2(THF)_2] initially give the adducts [(#eta#~5-C_5H_4R)(SPh)Ti(#mu#,#eta#~5-kS-C_5H_4P(S)Ph_2)(#mu#-SPh)Pt(C_6F_5)_2] [R = P(S)Ph_2 (1); SiMe_3 (4)], which finally rearrange in solution to form the double thiolate-bridged derivatives [(#eta#~5-C_5H_4R)(#eta#~5-C_5H_4P(S)Ph_2)Ti(#mu#-SPh)_2Pt(C_6F_5)_2] [R = P(S)Ph_2 (2) (syn); SiMe_3 (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(C_6F_5)_2(THF)_2] with [(#eta#~5-C_5H_4R)(#eta#~5-C_5H_4P(O)Ph_2)Ti(SPh)_2] (R = P(O)Ph_2; SiMe_3) only gives [(#eta#~5-C_5H_4R)(#eta#~5-C_5H_4P(O)Ph_2)Ti(#mu#-SPh)_2Pt(C_6F_5)_2] [R = P(O)Ph_2 (3) (syn); SiMe_3 (6) (syn/anti mixtures)] as expected due to the soft acid nature of the platinum centre.