Two new iridium�ruthenium cluster compounds Ir2Ru2(CO)11(EPh3)(�-H)3, (1a  , E = Sn, and 1b  , E = Ge) and IrRu3(CO)11(EPh3)3(�-H)4,(2a  , E = Sn, and 2b  , E = Ge) containing EPh3(E = Sn or Ge) ligands were obtained by the reaction of IrRu3(CO)13(�-H) with HSnPh3 and HGePh3, respectively. When compound 2b  was heated to 68 �C for 6h, two new compounds, IrRu3(CO)10( �-?2-C6H5)( �4-GePh)2, 3b  , and IrRu3(CO)9(�-?2-C6H5)( �4-GePh)2(�-GePh2), 4b  , were formed by cleavage of phenyl rings from the GePh3 ligands. Compounds 3b  and 4b  contain square IrRu3 clusters of the metal atoms with quadruply bridging GePh germylyne ligands on opposite sides of the cluster. Both compounds also contain a rare ?2-bridging phenyl ligand. Compound 4b  was found to react with dimethylacetylenedicarboxylate (DMAD) to yield the new compound IrRu3(CO)9([�4-Ge(Ph)C(CO2Me)C(CO2Me)](�-GePh2)2, 5  , by addition of DMAD to one of the bridging germylyne ligands. In the process the bridging phenyl ligand was transferred to the other bridging germylyne ligand to form a bridging germylene ligand. The compounds Ru4(CO)12(EPh3)2(�-H)4, (6a  , E = Sn, and 6b  , E = Ge) were obtained from the reactions of Ru4(CO)13(�-H)2 with HSnPh3 and HGePh3, respectively.. When heated, 6a   and 6b   were converted into the complexes Ru4(CO)12(�4-EPh)2, (6a  , E = Sn, and 6b  , E = Ge), by cleavage of two phenyl groups from each of the EPh3(E = Sn or Ge) ligands. The electronically unsaturated complex [Ru3(CO)8-(�3-CMe)(�-H)2(�3-H)]2 8  , viewed as a dimer of the 46-electronfragment Ru3(CO)8(�3-CMe)(�-H)3, is held together by delocalized bonding involving two triply bridging hydride ligands. Compound 8   exhibits a dynamic activity in solution that equilibrates two of the three types of hydride ligands. The bonding and electronic transitions of 7b   as wells as the unsaturated bonding in 8   were analyzed by DFT computational analyses.

Chemistry of high nuclearity ruthenium carbonyl cluster complexes with bridging group IV ligands

245th National Meeting (2013)

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