Reactions of [Os₃(μ-H)₂(CO)₁₀] with [Rh(COD)(L)I] (COD=cycloocta-1,5-diene; L=2,2′-bipyridine, 1,10-phenanthroline and 4,4′-diphenyl-2,2′-dipyridyl): Crystal and molecular structures of [Os₃Rh(μ-H)₃(CO)₁₀(η⁴-COD)]

The co-ordinatively unsaturated dihydride cluster [Os3(μ-H)2(CO)10] reacts with [Rh(COD)(L)I] (COD=cycloocta-1,5-diene; L=2,2′-bipyridine, 1,10-phenanthroline and 4,4′-diphenyl-2,2′-dipyridyl) to give a family of hydrido heterometallic clusters [Os3Rh(μ-H)3(CO)10(η4-COD)] 1, [Os3Rh(μ-H)2(CO)8(μ-CO)(μ-I)(η4-COD)] 2, [Os3Rh(μ-H)2(CO)8(μ-CO)(μ-I)(bipy)] 3, [Os3Rh(μ-H)2(CO)8(μ-CO)(μ-I)(1,10-phen)] 4, [Os3Rh(μ-H)2(CO)8(μ-CO)(μ-I)(4,4′-diphbipy)] 5 and [Os3(CO)12] in moderate yields. The crystal structures of 1-3 were established by X-ray diffraction method; 1 and 2 comprise a saturated tetrahedral Os3Rh core in which the rhodium atom is η4-co-ordinated by a COD ligand. In structure 3-5, a bidentate N-donor ligand chelates to the rhodium metal centre instead of the COD ligand. Clusters 1-5 were fully characterized by IR and1H-NMR spectroscopy, mass spectrometry and elemental analysis.