Aspects of the hydrogenation of carbon disulfide by transition-metal cluster compounds. The reactions of carbon disulfide with hydridotriosmium-carbonyl clusters
Reactions of CS/sub 2/ with H/sub 2/Os/sub 3/(CO)/sub 10/(Ia) and H/sub 2/Os/sub 3/(CO)/sub 9/(P(CH/sub 3/)/sub 2/C/sub 6/H/sub 5/) (Ib) are reported. To produce dicluster complexes (..mu..-S/sub 2/CH/sub 2/)(HOs/sub 3/(CO)/sub 9/L)/sub 2/ (L = CO, IIa; L = P(CH/sub 3/)/sub 2/C/sub 6/H/sub 5/, IIb). IIa has space group P1, a = 10.093 (3) A, ..beta.. = 13.289 (2) A, c = 13.865 (3) A, ..cap alpha.. = 84.53 (2)/sup 0/, b = 75.44(2)/sup 0/, ..gamma.. = 88.24 (2)/sup 0/, Z = 2, rho = 3.30 g/cm/sup 3/. IIa contains a methanedithiolato ligand linking two triosmium clusters. The S-C-S angle is tetrahedral. A dithioformato complex (..mu..-S/sub 2/CH)HOs/sub 3/(CO)/sub 9/(P(CH/sub 3/)/sub 2/C/sub 6/H/sub 5/) (IIIb) and a thioformaldehyde complex (..mu..-SCH/sub 2/)(..mu../sub 3/-S)Os/sub 3/(CO)/sub 9/(P(CH/sub 3/)/sub 2/C/sub 6/H/sub 5/) (IVb) were also isolated from the reaction of Ib with CS/sub 2/. IVb has space group P2/sub 1//c, a = 10.001 (2) A, b = 13.523 (3) A, c = 18.660 (5) A, ..beta.. = 91.26 (2)/sup 0/, Z = 4, rho = 2.74 g/cm/sup 3/. IVb contains a thioformaldehyde ligand which is ..pi.. bonded to one osmium atom C-S = 1.79 (1) A while the sulfur atom simultaneously serves as a bridge across two osmium atoms. It also contains a triply-bridging inorganic sulfide ligand in a cluster of three osmium atoms which has only one osmium-osmium bond. When heated, both IIIb and IVb decarbonylate to form the complex (..mu../sub 3/-eta/sup 2/-SCH/sub 2/)(..mu../sub 3/-S)Os/sub 3/(CO)/sub 8/(P(CH/sub 3/)/sub 2/C/sub 6/H/sub 5/) (Vb). Vb has space group P1, at -35/sup 0/C, a = 9.103 (4) A, b = 11.722 (4) A, c = 11.819 (2) A, ..cap alpha.. = 71.87 (2)/sup 0/, ..beta.. = 79.66 (2), ..gamma.. = 82.20 (3)/sup 0/, Z = 2, rho/sub calcd/ = 2.86 g/cm/sup 3/. Vb contains a triply-bridging thioformaldehyde ligand with the sulfur atom directly bridging two osmium atoms and the carbon atom bonded solely to the third. The C-S distance is 1.869 (6) A. Vb also contains a triply-bridging inorganic sulfide ligand, but unlike IVb the cluster has two osmium-osmium bonds.
- Research Organization:
- Yale Univ., New Haven, CT
- DOE Contract Number:
- ER-78-S-02-4900
- OSTI ID:
- 6644720
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 103:3
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON SULFIDES
CHEMICAL REACTIONS
OSMIUM COMPLEXES
CARBONYLS
CRYSTAL STRUCTURE
INTERATOMIC DISTANCES
ORGANIC SULFUR COMPOUNDS
PYROLYSIS
CARBON COMPOUNDS
CHALCOGENIDES
COMPLEXES
DECOMPOSITION
DISTANCE
ORGANIC COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties