The Iconoclastic Dynamics of the 1,2,6-Heptatriene Rearrangement

CASSCF(8,8)/6-31G* and AM1-SRP direct dynamics trajectory calculations have been run on the rearrangement of 1,2,6-heptatriene to 3-methylene-1,5-hexadiene. They show that the experimental results of Roth et al. on this reaction can be explained without the need to invoke a concerted, pericyclic mec...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2002-07, Vol.124 (27), p.7896-7897
Main Authors: Debbert, Stefan L, Carpenter, Barry K, Hrovat, David A, Borden, Weston Thatcher
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
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Summary:CASSCF(8,8)/6-31G* and AM1-SRP direct dynamics trajectory calculations have been run on the rearrangement of 1,2,6-heptatriene to 3-methylene-1,5-hexadiene. They show that the experimental results of Roth et al. on this reaction can be explained without the need to invoke a concerted, pericyclic mechanism. Instead, bifurcation occurs at the transition state for conversion of the reactant to 2-methylenecyclohexane-1,4-diyl. Some trajectories leaving the transition state do enter the PES local minimum for the intermediate, but others, differing only in the phases of the real-frequency vibrational modes, bypass the intermediate and proceed over a second transition state to the product. A significant fraction of the trajectories that do enter the biradical local minimum proceed on to the product in
ISSN:0002-7863
1520-5126
DOI:10.1021/ja026232a