Synthesis, Structure, and Catalytic Activity of Bimetallic Pt II –Ir III Complexes Bridged by Cyclooctane‐1,2‐dithiolato Ligands

Cationic Pt II –Ir III heterobimetallic complexes bridged by cyclooctane‐1,2‐dithiolato ligands [(PPh 3 ) 2 Pt(μ 2 ‐SRS)IrCl(η 5 ‐Cp*)][SbF 6 ] [R = cis ‐C 8 H 14 ( 5 ), trans ‐C 8 H 14 ( 6 ), Cp* = C 5 Me 5 ] were synthesized by reaction of (cyclooctane‐1,2‐dithiolato)Pt II complexes [Pt(SRS)(PPh 3 ) 2 ] [R = cis ‐C 8 H 14 ( 3 ), trans ‐C 8 H 14 ( 4 )] with [IrCl(μ‐Cl)(η 5 ‐Cp*)] 2 in thf in the presence of AgSbF 6 . The structures of complexes 5 and 6 were fully characterized by their NMR spectroscopic data. Moreover, X‐ray crystallographic analysis of 5 revealed that the PtS 2 Ir core exhibits a hinged arrangement, in which the cis ‐cyclooctane‐1,2‐dithiolate acts as a bridging ligand between the platinum and iridium metals. Complexes 5 and 6 served as a catalyst in the hydrosilylation of terminal alkynes R′CCH (R′ = Ph, Bu, CO 2 Me) with tertiary hydrosilanes such as Et 3 SiH and Ph 3 SiH to afford selectively β‐( Z )‐vinylsilanes 8 in high yields.