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Vibrationally Hot and Cold Triplets. Sensitizer-Dependent Dynamics and Localized Vibrational Promotion of a Di-π-methane Rearrangement
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2020-11-12 , DOI: 10.1021/jacs.0c10468
Kai-Yuan Kuan 1 , Daniel A Singleton 1
Affiliation  

Large intramolecular 13C 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.

中文翻译:

振动热和冷三胞胎。Di-π-甲烷重排的敏化剂依赖动力学和局部振动促进

当使用低能敏化剂时,苯并茚的二-π-甲烷重排的大分子内 13C 动力学同位素效应 (KIE) 符合重原子隧穿的统计预期,但使用高能敏化剂观察到的 KIE 低得多。这些结果与轨迹研究相结合表明,三重态能量转移中可用的多余振动能量导致重排中的热和非统计动力学。
更新日期:2020-11-12
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