Vibrationally Hot and Cold Triplets. Sensitizer-Dependent Dynamics and Localized Vibrational Promotion of a Di-π-methane Rearrangement.
| Autor: | Kuan KY; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842, United States., Singleton DA; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842, United States. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of the American Chemical Society [J Am Chem Soc] 2020 Nov 25; Vol. 142 (47), pp. 19885-19888. Date of Electronic Publication: 2020 Nov 12. |
| DOI: | 10.1021/jacs.0c10468 |
| Abstrakt: | Large intramolecular 13 C kinetic isotope effects (KIEs) for the di-π-methane rearrangement of benzobarrelene fit with statistical expectations from heavy-atom tunneling when a low-energy sensitizer is employed, but much lower KIEs are observed with higher-energy sensitizers. These results in combination with trajectory studies suggest that the excess vibrational energy available from triplet energy transfer leads to hot and nonstatistical dynamics in the rearrangement. |
| Databáze: | MEDLINE |
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