ORGN 79 |
| We have previously shown that dibenzothiophene-5-oxide (DBTO) undergoes deoxygenation upon photolysis forming O(3P) and dibenzothiophene. We are currently investigating the computed potential energy surfaces (PES) of thiophene-S-oxide (TO) and selenophene-Se-oxide (SeO) and the photochemistry of substituted TOs experimentally. The PESs of TO and SeO are being generated as a function of S-O and Se-O bond length using the CASSCF [18,14] method and include energy corrections with second order perturbation theory (MRMP2). The results for TO using MRMP2/G3Large*//MCSCF/6-31G(d) and SeO using MRMP2/6-31G(d)//MCSCF/6-31G(d) suggest that, unlike DBTO, the TO and SeO triplet states are higher in energy than the products of deoxygenation. We are currently locating the minimum energy crossing points at two surface crossings on the PES. In addition, we are investigating the spin-orbit coupling at the surface crossing points which will be used to estimate the Landau-Zener transition probability between states. |
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Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster
Division of Organic Chemistry |