Catalytic cyclooligomerization of thietane by trirhenium cluster complexes: A new route to polythiaether macrocycles
- Univ. of South Carolina, Columbia, SC (United States)
The trirhenium complex Re[sub 3](CO)[sub 10] [[mu]-SCH[sub 2]CH[sub 2]]([mu]-H)[sub 3] (1) reacts with dimethyl sulfide by a ring opening addition to the bridging thietane ligand to yield the zwitterionic complex Re[sub 3](CO)[sub 10][[mu]-SCH[sub 2]CH[sub 2]CH[sub 2]SMe[sub 2]]([mu]-H)[sub 3] (2) in 48% yield that contains a sulfonium-substituted thiolate ligand bridging an edge of the cluster. The structure of 2 was established by a single-crystal X-ray diffraction analysis. In this report, the results of our studies of the reactions of 1 with the thiaethers Me[sub 2]S and thietane, itself, are described. It is demonstrated that these thiaethers also produce ring opening of the bridging thietane ligand in 1, but in the case of thietane, a series of ring-opening coupling reactions occurs that is concluded by cyclization processes that yield polythiaether macrocycles. Indeed, the ring-opening cyclization can be performed catalytically under suitable conditions to yield the macrocycles in a free state in substantial amounts. 13 refs., 2 figs., 6 tabs.
- OSTI ID:
- 7080198
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:23; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360601 -- Other Materials-- Preparation & Manufacture
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ADDUCTS
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
DIMETHYL SULFIDE
LIGANDS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
POLYMERIZATION
RHENIUM COMPLEXES
SCATTERING
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION