Generation of Ir–Sn and Rh–Sn bonds from the oxidative addition of tin(IV) halides to [Ir(μ-Cl)(1,5-COD)]2 and [Rh(μ-Cl)(1,5-COD)]2

Facile oxidative addition of SnCl4, MeSnCl3, and SnBr4 across Ir(I) and Rh(I) cyclooctadiene complexes resulted in the formation of the corresponding Ir–Sn and Rh–Sn heterobimetallic complexes. Treatment of SnCl4 with [Ir(COD)(μ-Cl)]2 and [Rh(COD)(μ-Cl)]2 afforded [Ir(COD)(μ-Cl)Cl(SnCl3)]2 (1) and [Rh(COD)(μ-Cl)Cl(SnCl3)]2 (2), respectively. Reaction of the organotin halide MeSnCl3 with [Ir(COD)(μ-Cl)]2 led to the formation of [Ir(COD)(μ-Cl)Cl(MeSnCl2)]2 (3). The reaction of SnBr4 to IrI and RhI precursors gave [Ir(COD)(μ-Br)Br(SnBr3)]2 (4) and [Rh(COD)(μ-Br)Br(SnBr3)]2 (5) respectively, which indicates halide exchange at post-oxidative addition stage. The structures of complexes 1–5 were confirmed by X-ray crystallography. A cis-addition of Sn–X bond across IrI/RhI is proposed from the analysis of the geometrical features of “X–M–Sn” triangular units in 1–5.