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

Three new compounds, Ru4(mu4-GePh)2(mu-GePh2)2(mu-CO)2(CO)8 (11), Ru4(mu4-GePh)2(mu-GePh2)3(mu-CO)(CO)8 (12), and Ru4(mu4-GePh)2(mu-GePh2)4(CO)8 (13), were obtained from the reaction of H(4)Ru(4)(CO)12 with excess Ph(3)GeH in octane (11 and 12) or decane (13) reflux. Compound 11 was converted to compound 13 by reaction with Ph(3)GeH 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 Ru(4)Ge(2) group. Compound 11 also contains two edge-bridging GePh(2) groups on opposite sides of the cluster and two bridging carbonyl ligands. Compound 12 contains three edge-bridging GePh(2) groups and one bridging carbonyl ligand. Compound 13 contains four bridging GePh(2) groups, one on each edge of the Ru4 square. The reaction of H(4)Os(4)(CO)12 with excess Ph(3)GeH in decane at reflux yielded two new tetraosmium cluster complexes, Os4(mu4-GePh)2(mu-GePh2)3(mu-CO)(CO)8 (14) and Os4(mu4-GePh)2(mu-GePh(2))4(CO)8 (15). These compounds are structurally similar to compounds 12 and 13, respectively.