Qiang Zhang - Transformations of Triphenylgermyl Ligands in Iridium−Ruthenium Carbonyl Cluster Complexes

Version 1

      Publication Details (including relevant citation   information):

      Organometallics, 2011, 30 (2), pp 328–333

      DOI: 10.1021/om100989s

      Publication Date (Web): December 28, 2010

      Copyright © 2010 American Chemical Society

      Abstract:

      The new compound   IrRu3(CO)11(GePh3)3(μ-H)4,   1, was obtained in 64% yield from the reaction   of IrRu3(CO)13(μ-H) with HGePh3  at room temperature. Compound 1 has a butterfly   structure for the four metal atoms with three GePh3  ligands and four bridging hydride ligands around the periphery of   the cluster. When the reaction was performed at hexane reflux for   10 min, a second, minor compound,   Ir2Ru2(CO)11(GePh3)(μ-H)3,   2, was formed. Compound 2  contains a closed cluster having two iridium and two ruthenium   atoms, one GePh3 ligand, and three bridging hydride   ligands. When compound 1 was heated to 68 °C for   6 h, two new compounds,   IrRu3(CO)10(μ-η2-C6H5)(μ4-GePh)2,   3, and   IrRu3(CO)9(μ-η2-C6H5)(μ4-GePh)2(μ-GePh2),   4, were formed by cleavage of phenyl rings from   the GePh3 ligands. Compounds 3 and   4 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   η2-bridging phenyl ligand. Compound 4  was found to react with dimethylacetylenedicarboxylate (DMAD) to   yield the new compound   IrRu3(CO)9([μ4-Ge(Ph)C(CO2Me)C(CO2Me)](μ-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.

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