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It is possible that this deviation from linearity involves a change in mechanism. For example, a 1,5-hydrogen shift at higher temperature might be replaced by a catalyzed process with not only a lower enthalpy of activation, but also with a much more negative entropy of activation. Alternatively, a contribution from tunneling to the 1,5-hydrogen shift reaction that forms 9 from 4 could be responsible for the deviation from linearity seen in Figure 14A. This interpretation has precedent in the work of Truhlar and co-workers. Furthermore, Shizuka et al. have reported experimental and theoretical evidence for tunneling during their study of a similar 1,5-hydrogen shift in the photorearranged intermediate formed from N-acetylpyrrole. However, the very small H/D kinetic isotope effect of less than 3 at low temperatures does not seem to be consistent with a mechanism involving temperature-independent tunneling below 220 K.
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