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
- OSTI ID:
- 6644720
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:3; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON SULFIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DECOMPOSITION
DISTANCE
INTERATOMIC DISTANCES
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OSMIUM COMPLEXES
PYROLYSIS
SULFIDES
SULFUR COMPOUNDS
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPLEXES