Cluster synthesis. 33. New platinum-osmium carbonyl cluster complexes from Pt sub 2 Os sub 5 (CO) sub 17 (. mu. -H) sub 6 : Synthesis and characterization of PtOs sub 5 (CO) sub 15 (. mu. sub 3 -S)(. mu. -H) sub 6 , PtOs sub 5 (CO) sub 18 (. mu. -H) sub 4 , and PtOs sub 4 (CO) sub 15 (. mu. -H) sub 2

Journal Article · Wed Jul 10 00:00:00 EDT 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00014a015· OSTI ID:6069430

Adams, R D; Pompeo, M P; Wu, Wengan ^[1]

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1. Univ. of South Carolina, Columbia (United States)

From the reaction of Pt{sub 2}Os{sub 5}(CO){sub 17}({mu}{minus}H){sub 6} with H{sub 2}S at 25C the new platinum-osmium carbonyl cluster complex PtOs{sub 5}{minus}(CO){sub 15}({mu}{sub 3}{minus}S)({mu}{minus}H){sub 6} (2) was obtained in 83% yield. Compound 2 was characterized by ir, {sup 1}H NMR, {sup 13}C NMR, and single-crystal x-ray diffraction analyses. The structure of 2 consists of a PtOs{sub 3} tetrahedron fused to a PtOs{sub 2} triangle with the platinum atom at the vertex-sharing site. There is a triply bridging sulfido ligand on the PtOs{sub 2} triangular grouping. The molecule was shown by variable-temperature {sup 1}H NMR and {sup 13}C NMR spectroscopy to undergo a dynamic process that involves an intramolecular rotation of the Os{sub 2} triangular group relative to the Os{sub 2}S grouping at the platinum atom. {Delta}G {sub 261} = 12.3 kcal/mol. The reaction of Pt{sub 2}Os{sub 5}(CO){sub 17}({mu}-H){sub 6} with Os(CO){sub 5} at 25C yielded two new platinum-osmium carbonyl cluster complexes PtOs{sub 5}(CO){sub 18}({mu}{minus}H){sub 4} (3) and PtOs{sub 4}(CO){sub 15}({mu}{minus}H){sub 2} (4) in 38% and 25% yields, respectively. Both compounds were characterized crystallographically. The cluster of compound 3 consists of a PtOs{sub 5} tetrahedron fused to a PtOs{sub 2} triangle by the vertex-sharing platinum atom. The cluster of compound 3 contains a PtOs{sub 3} tetrahedron with an edge-bridging Os(CO){sub 4} group. The positions of all the hydride ligands in 3 and 4 were determined by a combination of {sup 1}H NMR spectroscopy and crystallography. Compound 3 is readily degraded by CO (25C/1 atm) to yield the products PtOs{sub 2}(CO){sub 10}, H{sub 2}Os{sub 2}(CO){sub 10}, H{sub 2}Os{sub 2}(CO){sub 8}, and H{sub 2}Os(CO){sub 4}. Crystal data for compound 2, 3, and 4 are presented. 12 refs., 3 figs., 10 tabs.

• OSTI ID: 6069430
• Journal Information: Inorganic Chemistry; (United States), Vol. 30:14; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
02 PETROLEUM
CARBONYLS
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
MOLECULAR STRUCTURE
HYDROGEN COMPOUNDS
OSMIUM COMPLEXES
PLATINUM COMPLEXES
SULFUR COMPOUNDS
CARBON 13
CATALYSIS
CATALYTIC EFFECTS
EXPERIMENTAL DATA
INFRARED SPECTRA
MONOCRYSTALS
NMR SPECTRA
PETROLEUM
PROTONS
REFORMER PROCESSES
X-RAY DIFFRACTION
BARYONS
CARBON ISOTOPES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTALS
DATA
DIFFRACTION
ELEMENTARY PARTICLES
ENERGY SOURCES
EVEN-ODD NUCLEI
FERMIONS
FOSSIL FUELS
FUELS
HADRONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUCLEONS
NUMERICAL DATA
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
020400 - Petroleum- Processing