Cluster synthesis. 36. New platinum-ruthenium and platinum-osmium carbonyl cluster complexes from the reactions of the complexes Pt sub 2 M sub 4 (CO) sub 18 (M = Ru, Os) with Cycloocta-1,5-diene in the presence of UV irradiation
- Univ. of South Carolina, Columbia (United States)
The reactions of Pt{sub 2}M{sub 4}(CO){sub 18} (1a, M = Ru; 1b, M = Os) with cycloocta-1,5-diene (COD) in the presence of UV irradiation were studied. The reaction of 1a yielded the new mixed-metal cluster compounds PtRu{sub 4}(CO){sub 12}({mu}{sub 4}-CO)(COD) (2) (11%) and Pt{sub 4}-Ru{sub 5}(CO){sub 20}(COD) (3) (16%). Compounds 2 and 3 were characterized by IR, {sup 1}H NMR, and single-crystal X-ray diffraction analyses. The cluster of 2 consists of a butterfly tetrahedron of four ruthenium atoms that is capped on one of the triangular faces by a Pt(COD) group. A {mu}{sub 4}-{eta}{sub 2}-CO ligand lies in the fold of the butterfly. The cluster of compound 3 consists of nine metal atoms and can be described as combination of a Pt{sub 3}Ru{sub 3} octahedron fused to a Pt{sub 3}Ru{sub 2} square pyramid with a common Pt{sub 3} face and a Pt(COD) capping group on the Ru{sub 3}face of the octahedron fused to a Pt{sub 3}Ru{sub 2} square pyramid with a common Pt{sub 3} face and a Pt(COD) capping group on the Ru{sub 3} face of the octahedron. The reaction of 1b yielded the hexanuclear products Pt{sub 2}Os{sub 4}(CO){sub 17} (5) (29%) and Pt{sub 2}Os{sub 4}(CO){sub 15}(COD) (6) (25%) and small amounts of the known hexanuclear products Pt{sub 2}Os{sub 4}(CO){sub 12}(COD){sub 2} (8) (6%) and PtOs{sub 2}(CO){sub 8}(COD) (4) (7%). Compound 6 was characterized crystallographically. The cluster of 6 exhibits the well-known triangle of triangles raft' structure with a Pt(COD) grouping on one of the outer triangles and one Pt(CO) group in the inner triangle. Compound 5 is believed to possess a structure similar to 6 but with two CO ligands in the place of the COD ligand. Cyclic voltammetric measurements on compound 5 showed the presence of two reversible one-electron reductions at E{sub 1/2} = {minus}0.57 and {minus}0.84 V. Compound 6 shows two quasireversible one-electron reductions at E{sub 1/2} = {minus}0.67 and {minus}0.93 V.
- OSTI ID:
- 7265817
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:25; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
020400 -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
BOND ANGLE
BOND LENGTHS
CARBONYLS
CATALYSTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHROMATOGRAPHY
COHERENT SCATTERING
COMPLEXES
CRYSTALS
CYCLOALKENES
DIFFRACTION
DIMENSIONS
ELECTROMAGNETIC RADIATION
ENERGY SOURCES
FOSSIL FUELS
FUELS
HYDROCARBONS
INDUSTRIAL PLANTS
INFRARED SPECTRA
LENGTH
LIGANDS
MONOCRYSTALS
NMR SPECTRA
ORGANIC COMPOUNDS
OSMIUM COMPLEXES
PETROLEUM
PETROLEUM REFINERIES
PLATINUM COMPLEXES
PROCESSING
RADIATIONS
REDUCTION
REFINING
RUTHENIUM COMPLEXES
SCATTERING
SEPARATION PROCESSES
SOLID CLUSTERS
SPECTRA
SYNTHESIS
THIN-LAYER CHROMATOGRAPHY
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET RADIATION
VOLTAMETRY
X-RAY DIFFRACTION