Iridium−Germanium and −Tin Carbonyl Complexes

The new compound Ir(COD)(CO)2GePh3, 1, was obtained when a solution containing [Ir(COD)Cl]2 and HGePh3 was treated with a solution of BuLi under a purge with CO. The tin homologue Ir(COD)(CO)2SnPh3, 2, was obtained similarly by replacing the HGePh3 reagent with HSnPh3. The reaction of [Ir(COD)Cl]2 with HGePh3 and CO in the absence of BuLi yielded the compound HIr(CO)3(GePh3)2, 3. When 3 was heated to reflux in toluene solvent, three new compounds were formed: Ir2(CO)6(GePh3)2(μ-GePh2), 4; H2Ir2(CO)4(GePh3)2(μ-GePh2)2, 5; and Ir2(CO)8[μ-Ph2Ge(OH)GePh2](μ-GePh2)(GePh3)2(μ-H), 6. The yield of 5 was increased when the reaction was performed under an atmosphere of hydrogen, and the yield of 4 was increased when the reaction was performed under an atmosphere of CO. The reaction of 4 with H2GePh2 yielded 5, 6, and the new compound H2Ir2(CO)4(μ-GePh2)(GePh2H)2, 7. Compounds 1−7 were fully characterized by IR, 1H NMR, and single-crystal X-ray diffraction analyses. Molecular orbital calculations on compounds 5 and 7 were performed and compared.