Multiple Additions of Phenylgermanium Ligands to Tetraruthenium and Tetraosmium Carbonyl Cluster Complexes

Three new compounds, Ru4(μ4-GePh)2(μ-GePh2)2(μ-CO)2(CO)8 (11), Ru4(μ4-GePh)2(μ-GePh2)3(μ-CO)(CO)8 (12),
and Ru4(μ4-GePh)2(μ-GePh2)4(CO)8 (13), were obtained from the reaction of H4Ru4(CO)12 with excess Ph3GeH in
octane (11 and 12) or decane (13) reflux. Compound 11 was converted to compound 13 by reaction with Ph3GeH
by heating solutions in nonane solvent to reflux. Compounds 11−13 each contain a square-type arrangement of
four Ru atoms capped on each side by a quadruply bridging GePh ligand to form an octahedral geometry for the
Ru4Ge2 group. Compound 11 also contains two edge-bridging GePh2 groups on opposite sides of the cluster and
two bridging carbonyl ligands. Compound 12 contains three edge-bridging GePh2 groups and one bridging carbonyl
ligand. Compound 13 contains four bridging GePh2 groups, one on each edge of the Ru4 square. The reaction of
H4Os4(CO)12 with excess Ph3GeH in decane at reflux yielded two new tetraosmium cluster complexes, Os4(μ4-GePh)2(μ-GePh2)3(μ-CO)(CO)8 (14) and Os4(μ4-GePh)2(μ-GePh2)4(CO)8 (15). These compounds are structurally
similar to compounds 12 and 13, respectively.