SYNTHESIS AND CHARACTERIZATION OF THE POLYOXOANION-SUPPORTED RU-I-RU-I TETRACARBONYLS [(P3O9)(2)RU-2(CO)(4)](4-) AND [(CP-ASTERISK-TIW5O18)(2)RU-2(CO)(4)](4-)

Five new Ru-I-Ru-I tetracarbonyl complexes, including two incorporating polyoxoanion ligands, have been prepared: [(P3O9)(2)RU(2)(CO)(4)](4-)(1), [(Cp*TiW5O18)(2)RU(2)(CO)(4)](4-)(2), [(CH3CN)(6)RU(2)(CO)(4)](2+)(3), [(PPh(3))(2)(CH3CN)(4)RU(2-) (CO)(4)](2+)(4), and [(C5H5N)(6)Ru-2(CO)(4)](2+)(5). Two of these complexes were structurally characterized in the solid state using single-crystal X-ray diffraction techniques: complex 1 as a solvated tetra-n-butylammonium salt [[(P3O9)(2)RU(2)(CO)(4)](TBA)(4.)2CH(3)CN: alpha=11.737(1) Angstrom, b=16.166(3)Angstrom, c=24.583(7)Angstrom, beta=100.19(2)degrees, Z = 2, space group P2(1)/c-C-2h(5)] and complex 4 as a hexafluorophosphate salt [[(PPh(3))(2)(CH3CN)(4)Ru-2(CO)(4)](PF6)(2): a=29.157(5)Angstrom, b=9.341(2)Angstrom, c=20.673(3)Angstrom, beta=108.40(5)degrees, Z = 4, space group C2/c-C-2h(6)]. The remaining were formulated and assigned structures on the basis of their elemental compositions, NMR spectra, and infrared spectra. Complex 3 proved to be a reactive precursor to a variety of Ru-I-Ru-I tetracarbonyl complexes, including complexes 1, 2, 4, and 5.