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

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