Catalysis and solvent participation in organometallic oxidative additions (Pt0→PtII and SnII→SnIV)

Abstract

The oxidative addition of (i) PhBr to SnR₂ or Sn(NR′₂)₂, or (ii) BuⁿCl to Sn(NR′₂)₂[R =(Me₃Si)₂CH, R′= Me₃Si] is catalysed by a trace of the more reactive halide EtBr, and when tetrahydrofuran is the solvent, rather than C₆H₆, a larger proportion of the product is the Sn^IV-dihalide rather than the Sn^IV–1 : 1 adduct; the solvent effect is also shown in the [Pt(PPh₃)₃]–MeI system, and both catalysis (for Pt⁰[graphic omitted]Pt^II by azobisisobutyronitrile) and solvent effects are interpreted in terms of radical-chain processes.