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1,3-hydrogen shift in propene radical cation: a facile antarafacial rearrangement

✍ Scribed by Minh Tho Nguyen; L. Landuyt; L.G. Vanquickenborne

Book ID: 103029595
Publisher: Elsevier Science
Year: 1991
Tongue: English
Weight: 558 KB
Volume: 182
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(91)80205-c

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✦ Synopsis

The 1,3-hydrogen shifts in both the r-ionized and neutral forms of propene are studied by ab initio MO calculations. Stationary points are located at the (U)MPZ level and relative energies calculated at the (U)MP4 level with the 6-31G(d, p) basis set. As in neutral propene. the migratory process in the propene radical cation takes place antarufuciul/y via a C&an&ion structure. Upon x-ionization, the barrier height is reduced from 358 to 139 kJ/mol. Such a remarkable effect arises from a weakened carbon-hydrogen bond and a more favourable orbital interaction in the ionized transition structure. The distribution of localized orbital centroids in the transition structures suggests that the 1,3_sigmatropic rearrangement involves a hydride transfer in Kionized propene and a proton transfer in neutral propene.

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