ORGN 456 |
| Encouraged by the recent laboratory detection of butatrienethione 1, a potential interstellar molecule, we initiated matrix isolation studies on the cumulene 1 with aid of UV and IR spectroscopy. During the course of the studies, we found an apparent photoreversible isomerization process, a (1,3) hydrogen shift, between 1 and ethynylthioketene 2. Coupled cluster calculations at the level of CCSD(T)/cc-pVTZ reveal that the two photoreversible isomers are almost degenerate in energy and indeed are global minima along the C4H2S potential energy surface (PES). In this presentation, we also describe ongoing efforts to prepare ethynylthiirene 3, a formal antiaromatic C4H2S isomer, and to deposit it in an Ar matrix, which would provide mechanistic insight into its versatile isomerization manifold along the C4H2S PES.
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New Reactions, Methodology, Total Synthesis, Physical Organic Chemistry
8:00 PM-10:00 PM, Tuesday, 15 March 2005 Convention Center -- Sails Pavilion, Poster
Division of Organic Chemistry |
