Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 36, Pages 10746-10749Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201704787
Keywords
IR spectroscopy; isotopes; matrix isolation; rearrangement; solid-state reactions
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Funding
- Cluster of Excellence RESOLV - Deutsche Forschungsgemeinschaft (DFG) [EXC 1069]
- Robert A. Welch Foundation [B0027]
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As an experimental test of the theoretical prediction that heavy-atom tunneling is involved in the degenerate Cope rearrangement of semibullvalenes at cryogenic temperatures, monodeuterated 1,5-dimethylsemibullvalene isotopomers were prepared and investigated by IR spectroscopy using the matrix isolation technique. As predicted, the less thermodynamically stable isotopomer rearranges at cryogenic temperatures in the dark to the more stable one, while broadband IR irradiation above 2000 cm(-1) results in an equilibration of the isotopomeric ratio. Since this reaction proceeds with a rate constant in the order of 10(-4) s(-1) despite an experimental barrier of E-a = 4.8 kcal mol(-1) and with only a shallow temperature dependence, the results are interpreted in terms of heavy-atom tunneling.
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