Cluster syntheses. 14. The syntheses and structural characterization of the high-nuclearity sulfidoruthenium carbonyl cluster compounds Ru/sub 5/(CO)/sub 14/(. mu. /sub 4/-S)/sub 2/, Ru/sub 6/(CO)/sub 17/(. mu. /sub 4/-S)/sub 2/, and Ru/sub 7/(CO)/sub 20/(. mu. /sub 4/-S)/sub 2/

Journal Article · Wed Aug 26 00:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00264a017· OSTI ID:5648615

Adams, R D; Babin, J E; Tasi, M

The reaction of Ru/sub 3/(CO)/sub 9/(..mu../sub 3/-S)/sub 2/ (2) with Ru/sub 3/(CO)/sub 12/ under UV irradiation has yielded the higher nuclearity cluster compounds Ru/sub 4/(CO)/sub 9/(..mu..-CO)/sub 2/(..mu../sub 4/-S)/sub 2/ (3), 38%, Ru/sub 5/(CO)/sub 14/(..mu../sub 4/-S)/sub 2/ (4), 20%, and Ru/sub 6/(CO)/sub 17/(..mu../sub 4/-S)/sub 2/ (5), 3%. Thermal decarbonylation of Ru/sub 3/(CO)/sub 9/(..mu../sub 3/-CO)(..mu../sub 3/-S) (1) at 100/sup 0/C has yielded 3, 47%, 5, 10%, and Ru/sub 7/(CO)/sub 20/(..mu../sub 4/-S)/sub 2/ (6), 26%. The large clusters are decomposed to 2 and 3 by reaction with CO at 1 atm. Compounds 4-6 have been characterized by single-crystal X-ray diffraction analyses. For 4: space group P2/sub 1//n, a = 8.787 (2) A, b = 14.550 (3) A, c = 19.741 (3) A, ..beta.. = 98.09 (1)/sup 0/, Z = 4, rho/sub calcd/ = 2.56 g/cm/sup 3/. The cluster consists of an approximately square arrangement of four ruthenium atoms with quadruply bridging sulfido ligands on each face. An Ru(CO)/sub 4/ unit bridges one Ru-Ru edge of the cluster. But the EAN rule the molecule is unsaturated, and one of the Ru-Ru bonds was found to be unusually short, 2.704 (1) A. For 5: space group P2/sub 1/2/sub 1/2/sub 1/, a = 11.211 (2) A, b = 14.666 (4) A, c = 17.611 (4) A, Z = 4, rho/sub calcd/ = 2.63 g/cm/sup 3/. Compound 5 is isomorphous and isostructural with the know osmium homologue. The molecule consists of a pentagonal-bypyramidal cluster of five ruthenium atoms with two sulfido ligands. A Ru(CO)/sub 4/ group bridges one apical-equatorial edge of the cluster. For 6: space group P2/sub 1/2/sub 1/2/sub 1/, a = 11.226 (3) A, b = 14.320 (4) A, c = 21,217 (5) A, Z = 4, rho/sub calcd/ = 2.59 g/cm/sup 3/. Compound 6 is isomorphous and isostructural with the known osmium homologue. The molecule consists of a pentagonal-bipyramidal cluster of five ruthenium atoms and two sulfido ligands. Two Ru(CO)/sub 4/ groups bridge symmetrically adjacent apical-equatorial edges of the cluster.

• Research Organization: Univ. of South Carolina, Columbia
• OSTI ID: 5648615
• Journal Information: Inorg. Chem.; (United States), Vol. 26:17
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
MOLECULAR STRUCTURE
RUTHENIUM COMPOUNDS
SULFIDES
EXPERIMENTAL DATA
SPACE GROUPS
X-RAY DIFFRACTION
CHALCOGENIDES
COHERENT SCATTERING
DATA
DIFFRACTION
INFORMATION
NUMERICAL DATA
REFRACTORY METAL COMPOUNDS
SCATTERING
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties