Transformations of thiacyclohexane by a triosmium cluster
- Univ. of South Carolina, Columbia, SC (United States)
The reactions of thiacyclohexane (TCH) with Os[sub 3](CO)[sub 10](NCMe)[sub 2], Os[sub 3](CO)[sub 11](NCMe), and Os[sub 3](CO)[sub 12] have been investigated. The reaction of TCH with Os[sub 3](CO)[sub 10](NCMe)[sub 2] at 25[degree]C yielded the disubstituted product Os[sub 3](CO)[sub 10](TCH)[sub 2], 1, in 86% yield. At 97[degree]C, compound 1 was transformed into four new compounds: Os[sub 3](CO)[sub 9]([mu]-[bar S]CH[sub 2]CH[sub 2]CH[sub 2]CH[sub 2]C)([mu]-H)[sub 2], 2 (20%), Os[sub 3](CO)[sub 8]([mu]-[bar S]CH[sub 2]CH[sub 2]CH[sub 2]C) [S(CH[sub 2])[sub 5]] ([mu]-H)[sub 2], 3 (4%), Os[sub 3](CO)[sub 11]([bar S]CH[sub 2]CH[sub 2]CH[sub 2]CH[sub 2]CH[sub 2]), 4 (15%), and Os[sub 3](CO)[sub 9]([mu]-[bar S]CH[sub 2]CH[sub 2]CH[sub 2]CH[sub 2]CH)([mu]-H), 5 (13%). Compounds 2, 3, and 5 were characterized by single crystal X-ray diffraction analysis. These three products were formed by the loss of one TCH ligand. In compounds 5 and 2 the remaining TCH ligand has undergone activation of one and two CH bonds, respectively, [alpha] to the sulfur atom and the TCH ligand was transformed into a metalated triply bridging ligand. Compounds 2 and 5 are interconvertible isomers. Compounds 2, 3, and 5 were also obtained from the pyrolysis of 4 at 97[degree]C and from the reaction of Os[sub 3](CO)[sub 12] with TCH at 125[degree]C. 23 refs., 3 figs., 10 tabs.
- OSTI ID:
- 5065165
- Journal Information:
- Organometallics; (United States), Vol. 12:12; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
HETEROCYCLIC COMPOUNDS
CHEMICAL REACTIONS
X-RAY SPECTRA
OSMIUM COMPLEXES
SULFUR COMPOUNDS
CARBONYLS
COMPILED DATA
CRYSTAL STRUCTURE
LIGANDS
ORGANOMETALLIC COMPOUNDS
SOLID CLUSTERS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
SCATTERING
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
665000 - Physics of Condensed Matter- (1992-)