Abstract The activation of Ph3GeH at the dppm-bridged cluster Ru3(CO)10(μ-dppm) [dppm = bis(diphenylphosphino)methane] has been investigated. Ru3(CO)10(μ-dppm) reacts with Ph3GeH at room temperature in the presence of Me3NO to give the new… Click to show full abstract
Abstract The activation of Ph3GeH at the dppm-bridged cluster Ru3(CO)10(μ-dppm) [dppm = bis(diphenylphosphino)methane] has been investigated. Ru3(CO)10(μ-dppm) reacts with Ph3GeH at room temperature in the presence of Me3NO to give the new cluster products Ru3(CO)9(GePh3)(μ-dppm)(μ-H) (1) and Ru3(CO)8(GePh3)2(μ-dppm)(μ-H)2 (2) via successive oxidation-addition of two Ge–H bonds. Refluxing 1 in THF furnishes the diruthenium complex Ru2(CO)6(μ-GePh2)(μ-dppm) (3) as the major product (44%), in addition to Ru3(CO)7(μ-CO)(GePh3){μ3-PhPCH2P(Ph)C6H4}(μ-H) (4) and the known cluster Ru3(CO)9(μ-H)(μ3-Ph2PCH2PPh) (5) in 7 and 8% yields, respectively. Heating samples of cluster 2 also afforded 3 as the major product together with a small amount of Ru3(CO)7(GePh3)(μ-OH)(μ-dppm)(μ-H)2 (6). DFT calculations establish the stability of the different possible isomers for clusters 1, 2, and 6, in addition to providing insight into the mechanism for hydride fluxionality in 2. All new compounds have been characterized by analytical and spectroscopic methods, and the molecular structures of 1, 3, and 6 have been established by single-crystal X-ray diffraction analyses.