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SnCl2 insertion into Ir–Cl and Rh–Cl bonds: Synthesis, characterization and catalytic activity of three-legged piano-stool trichlorostannyl iridium and rhodium complexes

Journal of Organometallic Chemistry
DOI: 10.1016/j.jorganchem.2014.06.011
  • Catalyst
  • Bimetallic
  • Iridium
  • Rhodium
  • Alkylation


Abstract Facile insertion reaction of SnCl2 across pentamethylcyclopentadienyl complexes of Ir(III) and Rh(III) resulted in the formation of Ir–SnCl3 and Rh–SnCl3 heterobimetallic complexes. Treatment of SnCl2 with [Cp*IrCl2]2 and [Cp*Ir(NH2tBu)Cl2] afforded [Cp*Ir(SnCl3)2{SnCl2(H2O)2}] (1) and [Cp*Ir(SnCl3)3][NH3tBu] (3), respectively. Similarities in NMR data for complexes 1 and 3 suggested that complex 1 converts to anionic [Cp*Ir(SnCl3)3] species in solution via rapid chloride exchange. Similarly, insertion reaction of SnCl2 with [Cp*Ir(PPh3)Cl2] and [Cp*Rh(PPh3)Cl2] afforded single insertion complex [Cp*Ir(PPh3)(SnCl3)Cl] (2) and double insertion complex [Cp*Rh(PPh3)(SnCl3)2] (4), respectively. All these new complexes were characterized by multinuclear NMR spectroscopy, while complexes 1, 3 and 4 were structurally characterized by single crystal X-ray diffraction technique. Complexes 1–4 were also tested as catalyst for bisarylation of aldehyde with arene and it was observed that only complexes 1 and 3 were active. Scope of this organic reaction was examined for different arenes and heteroarenes and in all the cases very good yields of triarylmethane derivatives were achieved.

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