A highly efficient secondary benzylation procedure has been demonstrated using a high- valent heterobimetallic complex [Ir2 (COD) 2 (SnCl3) 2 (Cl) 2 (μ-Cl) 2] 1 as the catalyst in 1, 2-dichloroethane to afford the corresponding benzylated products in moderate to excellent yields. The reaction was performed not only with carbon nucleophiles (arenes and heteroarenes) but also with oxygen (alcohol), nitrogen (amide and sulfonamide), and ...