Reactions of Bis(chalcogenolato) Complexes [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(CO)(ETol)<sub>2</sub>] (E = Se, S; Tol = <i>p</i>-Tolyl) with [Pt(PPh<sub>3</sub>)<sub>3</sub>]. Formation of Tri- or Dinuclear Mixed-Metal Complexes with Bridging Chalcogenido or Chalcogenolato Ligands
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Treatment of [Cp*Ir(CO)(SeTol)2] (Cp* = η5-C5Me5, Tol = p-tolyl) with 2 equiv of [Pt(PPh3)3] in toluene at reflux resulted in the insertion of Pt(PPh3) groups into Se−Tol bonds to give the triangular cluster with capped Se ligands [Cp*Ir(μ3-Se)2{PtTol(PPh3)}2] (5). By stirring under CO atmosphere, 5 in solution was readily converted to [Cp*Ir(CO)(μ3-Se)2{PtTol(PPh3)}2] (2b), which returned to 5 in toluene at reflux. On the other hand, reaction of [Cp*Ir(CO)(STol)2] with an equimolar amount of [Pt(PPh3)3] afforded the thiolato-bridged dinuclear complex [Cp*Ir(CO)(μ-STol)Pt(STol)(PPh3)] (6) through the insertion of the Pt center into the Ir−S bond, and that with 2 equiv of [Pt(PPh3)3] in toluene at reflux led to the incorporation of the second Pt fragment to the core of 6 to give the thiolato-bridged triangular cluster [Cp*Ir{Pt(PPh3)}2(μ2-CO)(μ2-STol)2] (7). An X-ray diffraction study has been carried out to determine the detailed structures of 2b, 5, 6, and [Cp*Ir{Pt(PPh3)}2(μ2-CO)(μ2-SPh)2], which is the SPh analogue of 7.
