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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

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00025a009· OSTI ID:7265817
; ; ;  [1]
  1. 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