CHEMISTRY OF HEXARUTHENIUM CARBIDOCARBONYL CLUSTER COMPLEXES - SYNTHESES AND X-RAY CRYSTAL-STRUCTURES OF RU6C(CO)15(MU-SEPH)(MU-AUPPH3), RU6C(CO)14(MU-SEPH)2, AND RU6C(CO)14(MU-SEPH)(MU,ETA-3-C3H5)

Treatment of [PPN]2[Ru6C(CO)16] (PPN = (PPh3)2N) (1) with phenylselenenyl chloride at room temperature yields [PPN][RU6C(CO)15(SePh)] (2a). Reaction of 2a with AuClPPh3 in the presence of silver tetrafluoroborate affords Ru6C(CO)15(SePh)(AuPPh3) (3), which has edge bridging SePh and AuPPh3 ligands. Heating of 2a under reflux in bis(2-methoxyethyl) ether yields Ru6C(CO)14(SePh)2 (4) with two edge bridging SePh ligands. Reaction of 2a with allyl bromide at 110-degrees-C gives an allyl cluster Ru6C(CO)14(SePh)(C3H5) (5) in which the allyl ligand coordinates to a metal-metal edge in a mu,eta-3-manner and the SePh ligand bridges another edge. The structures of 3, 4, and 5 have been determined by single crystal X-ray diffraction studies.