Externally sensitized mesolytic fragmentations in dithiane-ketone adducts |
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Authors: | Tiffany P. Gustafson |
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Affiliation: | Department of Chemistry and Biochemistry, University of Denver, Denver, CO 80208-2436, USA |
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Abstract: | The apparent activation enthalpies, ΔH≠, for externally sensitized mesolytic fragmentations in benzophenone-dithiane adducts were obtained in variable temperature photolyses and compared with DFT activation barriers calculated for β-scission in the corresponding oxygen-centered radicals. The results of these experimental and theoretical studies further support the mechanism in which deprotonation of the hydroxy-group, in the transient cation radical, is coupled with intramolecular electron transfer furnishing the O-centered radical, which subsequently fragments. The quantum yields of fragmentation increase for higher alkyl substituted dithiane adducts. |
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